TW526488B

TW526488B - Molecular level optical information storage devices

Info

Publication number: TW526488B
Application number: TW089123254A
Authority: TW
Inventors: Carlo Alberto Bignozzi; Patrick Sanders
Original assignee: Molecular Storage Technologies
Priority date: 1999-11-04
Filing date: 2000-11-24
Publication date: 2003-04-01
Also published as: WO2001048751A3; WO2001048751A9; AU5287101A; WO2001048751A8; WO2001048751A2

Abstract

The present invention relates to use of transition metal complexes in photochromic devices, to the production of optical information storage devices based on a polymeric matrix and on metal oxides with adsorbed transition metal complexes, to the production of photochromic materials constituted by a film of metal oxide with adsorbed two different type of molecular systems, one acting as a charge transfer sensitizer and the second as an electron acceptor.

Description

526488 A7 -------B7 _ 五、發明說明（）發明領嫉：本發明係關於使用過渡金屬錯合物為手段於光學資料儲存裝置中儲存資料。登_明背景：現今大部分研究致力於可呈現兩種形式的雙穩態分子或超分子物種，其互換現象可藉由外界刺激劑予以調整控制（Lehn J· M.，Supramolecular Chemistry, Concepts and Perspectives VCH: Weiheim，（1 995))，此種分子能階切換裝置之設計係直接連結至訊號產生、轉移、轉換、儲存及偵測化學。傳統的雙穩態物種包含光致變色化合物，這些分子可在呈現不同可見光吸收（例如，顏色）的兩種形式之間互相變換，光致變色現象（photochromsim)發生於不同材料種類，包含無機與有機兩種化合物，有機化合物之種類如苯胺類、二硫氧類、腙類、噁嗪酮、半卡巴腙、反二苯代乙烯衍生物、丁二酸酐、樟腦衍生物、综合及螺旋狀化合物，而無機化合物有更多種類顯現光致變色現線，包含金屬氧化物、鹼土金屬硫化物、鈦酸鹽類、汞化合物及銅化合物，這些材料為習知已久且可在文獻中找到這些系統詳細資料。（“Photochromism” Glenn H· Brown Ed·，Volume III，John Wiley & Sons, Publisher, 1971) 因其在兩種不同顏色之間互換’所以光致變色化合物具有能力作為二元資料儲存系統，一種顏色表示0而第二第2頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 0--------訂---------線經濟部智慧財產局員工消費合作社印製 526488 ____ A7 --------— R7___ 五、發明說明（）種顏色表示1用以將資料編碼為數位形式，分子能階光學記憶7C件加上這些分子應可使極大量資料包裝於小空間，並透過具有奈米（nan〇meter)級解析度之二元碼讀取。然而’前述習知的光致變色化合物不適用於長期資料儲存’當其保存於黑暗中時，大部分光致變色化合物藉由光激發改變顏色並回復至原來狀態，但多少有些授，化合物顯現這些特性對於儲存資料是無用的，因為這些已寫入資料在經過相當短時間之後即自然地消除。其他習知光致變色化合物較穩定，但傾向於進行可回復的光異構化（Irie，M·; Mohri，M. J. Org. Chem. 53, 803 (1988); Hanazawa，Μ·; Sumiya，R·; Horikawa，Υ·; Irie，M; J· Chem. Soc· Chem.526488 A7 ------- B7 _ 5. Explanation of the invention () The invention is enlightened: The present invention relates to the use of transition metal complexes as a means to store data in optical data storage devices. Background: Most researches today focus on two forms of bistable molecules or supramolecular species, and the exchange phenomenon can be adjusted and controlled by external stimulants (Lehn J. M., Supramolecular Chemistry, Concepts and Perspectives VCH: Weiheim, (1 995)), the design of this molecular energy level switching device is directly connected to signal generation, transfer, conversion, storage and detection chemistry. Traditional bistable species contain photochromic compounds. These molecules can transform between two forms that exhibit different visible light absorption (eg, color). Photochromsim occurs in different types of materials, including inorganic and Two organic compounds. Types of organic compounds such as anilines, dithioxides, amidines, oxazinone, hemicarbazone, transdiphenylethylene derivatives, succinic anhydride, camphor derivatives, comprehensive and spiral compounds There are more types of inorganic compounds that show photochromic appearance, including metal oxides, alkaline earth metal sulfides, titanates, mercury compounds, and copper compounds. These materials are well known and can be found in the literature. Details. ("Photochromism" Glenn H. Brown Ed., Volume III, John Wiley & Sons, Publisher, 1971) Photochromic compounds have the ability to act as binary data storage systems because they are interchangeable between two different colors. The color indicates 0 and the second page 2 This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 0 -------- Order --------- Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 526488 ____ A7 ------------ R7___ V. Description of the invention () Color indication 1 is used to encode the data as In digital form, 7C pieces of molecular energy optical memory plus these molecules should allow a very large amount of data to be packed in a small space and read through a binary code with nanometer-level resolution. However, 'the aforementioned conventional photochromic compounds are not suitable for long-term data storage'. When stored in the dark, most photochromic compounds change color and return to their original state by light excitation, but the compounds appear somewhat These characteristics are useless for storing data, because the written data is naturally eliminated after a relatively short period of time. Other conventional photochromic compounds are relatively stable but tend to undergo reversible photoisomerization (Irie, M ·; Mohri, MJ Org. Chem. 53, 803 (1988); Hanazawa, M ·; Sumiya, R ·; Horikawa , Υ ·; Irie, M; J · Chem. Soc · Chem.

Commun. 208 (1992); Saika, T; Irie, M; Shimidzu, T; J. Chem. Soc. Chem· Commun. 2123 (1994))，此種化合物可用於資料儲存光電元件，但無法提供良好的長期儲存解決方法，因為用於讀取已寫入數據的光會造成被取樣分子後向變換，而漸漸流失資料，許多嘗試已被用於克服此困難，包含使用光化學惰性紅外光讀取系統狀態等。因此，有必要改良光致變色分子，以提供穩定的且長本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------^------1—^ ----------------------- (請先閱讀背面之注意事項再填寫本頁) 存儲料資的期經濟部智慧財產局員工消費合作社印製Commun. 208 (1992); Saika, T; Irie, M; Shimidzu, T; J. Chem. Soc. Chem. Commun. 2123 (1994)), this compound can be used for data storage optoelectronic components, but does not provide good Long-term storage solution, because the light used to read the written data will cause the sampled molecules to transform backwards and gradually lose data. Many attempts have been used to overcome this difficulty, including the use of photochemically inert infrared light reading systems Status, etc. Therefore, it is necessary to improve the photochromic molecules in order to provide a stable and long paper size applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -------- ^ ------ 1— ^ ----------------------- (Please read the precautions on the back before filling out this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs who store materials Printed by Consumer Cooperatives

述概及的 0 明發I 不且定穩行進下件條制控在種物性應反供提明發本缺之子分色變致光中術技知習月克以化變色顏的逆。可點 3 第 526488In summary, 0 Mingfa I must proceed steadily. The control of the physical properties of the seeds should be provided to the child who knows the color separation of the child who is lacking the hair color. The technique of photoneutralization is used to reduce the inversion of color. May 3rd 526488

經濟部智慧財產局員工消費合作社印製Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

本發明之一特點為提供二元資料記錄媒介包含一基材及一圮錄層於基材上，記錄層包含一有機金屬的過渡金屬錯合物其吸收第一波長，當錯合物為一光感應激發態結果產生反應產物於記錄層，其吸收第二且不同波長的光。第一波長的光吸收值疋為第一數值，而第二波長的光吸收值定為第二數值，第一數值及第二數值對應為二.元碼。過渡金屬錯合物為本發明之一特點，其包含至少下列分子式之一：[M(N-N)2L2]n、[M(N-N)L4]n、[M(N-N-N)L3]n 及 [M(N-N-N)2]n ’ Μ為一過渡金屬；N-N為發色團的聚毗啶配合基結合選自下列群組之一至二個取代基包含：-C〇〇H、 -b(oh)2、-Ρ03Η2及-R-P〇3h2，其中R為一飽和或一芳香碳氫化合物；N-N-N為發色團的三说淀配合基結合選自下列群組之一至三個取代基包含：<0011、-8(011)2、-P〇3H2、-R-POsH2及苯基，其中苯基結合一個或更多個選自下列群組取代基包含：-COOH、-B(0H)2、-P〇3H2及-R-P〇3H2，其中R為一飽和或.一芳香碳氫化合物；L為非發色團的單齒或多齒附屬配合基。此特別實施例之其他特點為Μ係選自鈷、鎳、銅、銥、鈀、鉑、鍊、鐵、鐵、釕及鍺；Ν-Ν係選自取代與未取代的2,2’·二毗啶基、取代與未取代的1，10-二氮雜菲以及取代或未取代的2,2、二喳啉；Ν-Ν-Ν係被苯基取代，且苯基結合一取代基於對位上；L係選自NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、NCS-、N3-、-CH3-、IT、草酸基、CO、CN-、NO、H20、OH-、NH3、***、吡啶、第4頁One feature of the present invention is to provide a binary data recording medium including a substrate and a recording layer on the substrate. The recording layer includes an organometallic transition metal complex which absorbs the first wavelength. When the complex is a As a result of the light-induced excited state, a reaction product is generated in the recording layer, which absorbs light of a second and different wavelength. The light absorption value 疋 of the first wavelength is a first value, and the light absorption value of the second wavelength is set to a second value, and the first value and the second value correspond to a binary code. A transition metal complex is a feature of the present invention and includes at least one of the following molecular formulas: [M (NN) 2L2] n, [M (NN) L4] n, [M (NNN) L3] n, and [M ( NNN) 2] n′M is a transition metal; NN is a polypyridine ligand of a chromophore in combination with one or two substituents selected from the group consisting of: -COOH, -b (oh) 2, -P03Η2 and -RP〇3h2, in which R is a saturated or an aromatic hydrocarbon; NNN is a chromophore, said three complexes are selected from one of the following groups to three substituents containing: < 0011,- 8 (011) 2, -P〇3H2, -R-POsH2, and phenyl, wherein the phenyl group combines one or more substituents selected from the group consisting of: -COOH, -B (0H) 2, -P. 3H2 and -RP03H2, where R is a saturated or .aromatic hydrocarbon; L is a non-chromophore monodentate or multidentate accessory ligand. Other features of this particular embodiment are that M is selected from cobalt, nickel, copper, iridium, palladium, platinum, chain, iron, iron, ruthenium, and germanium; N-N is selected from substituted and unsubstituted 2,2 '· Dipyrimidinyl, substituted and unsubstituted 1,10-diazaphenanthrene, and substituted or unsubstituted 2,2 bisphosphonline; N-N-N is substituted by phenyl, and phenyl bond-substitution is based on On the para position; L is selected from NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halo, NCS-, N3-, -CH3-, IT, Oxalate, CO, CN-, NO, H20, OH-, NH3, triazole, pyridine, page 4

! I I ! I t--1ΙΙΙΙΙ-Ί 垂！ IIIII!--I, (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） 526488 A7 B7 五、發明說明（）對二氮雜苯、4,4，-二毗啶、4,4’-二毗啶基乙烷、4,4’-二说淀基乙烯、4 -氰也淀、二苯甲腈、對二氮己環、N〇2及乙醯丙酮；或者L可包含一配位溶劑選自下列族群包含：乙醯丙酮、甲醇、氰甲烷、丙酮、四氫呋喃、乙醇、二甲基甲醯胺及二甲基氧硫基’基材可為非晶形、微結晶或半導體。 ♦ 本發明另一特點為過渡金屬錯合物包含至少了列之一分子式·· [M(N-N)2(Y_nor-Y)(L)]n、[Μ(Ν_Ν)2(Υ-π〇Γ-Υ)2]η、 [M(N-N)2(X)(Y-nor-Y)M(N-N)2(L^n ' [M(N-N-N)(Y-nor-Y)(L)2]n ' [M(N-N-N)2(Y-n〇3>Y)2(L)]n 及[M(N-N-N)2(L)2(Y-nor-Y)M(N-N-N)2(L)2]n，Y係選自氰基、说淀、11比淀亞甲基，而n〇r為正菠二烯；Μ為過渡金屬；N-N為取代或未取代的發色團聚毗啶配合基；Ν-Ν-Ν為取代與未取代的發色團三也淀配合基；L為非發色團的單齒或多齒附屬配合基；X為係選自下列族群之一包含··聚氮雜大環族及聚硫代大環族。本發明另一特點為過渡金屬錯合物包含至少下列之一分子式：[trans-HOOCpyRun(X)4-NC-nor-CN]2+、{[trans-HOOCpyRun(X)4-NC]2-nor}4+、[trans-CH3-OOCpyRun(X)4-NC-nor-CN]2+ > {[trans-CH3-OOCpyRun(X)4-NC]2-nor]4+ ' [trans-CH3CH2-OOCpyRuH(X)4.NOnor-CN]2+ 及{[trans-CH3CH2-OOCpyRun(X)4-NC]2-nor]4+，HOOCpy為異菸鹼酸；NC-no卜CN為二氰正菠二烯配合基；X係選自聚氮雜大環族、聚硫代大環族及NH3 ; trans為以釕（Ru)為中心之結構。本發明另一特點為過渡金屬錯合物包含一分子感光第5頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填寫本頁) # 訂---------旅經濟部智慧財產局員工消費合作社印製 r526488 ___ A7 ---------- B7___ 五、發明說明（) (請先閱讀背面之注意事項再填寫本頁) 劑’分子感光劑具有一光吸收光譜及能夠射出一電子進入基材2的傳導帶，在可見光吸收值上，以形成氧化分子感光劑，其具有不同於未氧化分子感光劑之光吸收光譜，一電子接收劑顯現其具有一光吸收光譜及能夠由一還原的電子接收劑接受電子，其具有不同的光吸收光譜，氧化分子感光劑及還原分子感光劑之間電荷分離維持在持續照射可見光。在此特點中過渡金屬以下列至少一分子式表示： [M(N-N)2L2]n、[M(N-N)L4]n、[M(N-N-N)L3]n &[Μ(Ν-Ν-Ν)2]η，Μ 為一過渡金屬；N-N為發色團的聚吡啶配合基及結合選自下列群組之一至二個取代基包含：-C〇〇H、·β(0Η)2、-POsH2及-R-P〇3h2，其中r為一飽和或一芳香碳氫化合物；N-N-N為發色團的三吡啶配合基結合選自下列群組之一至三個取代基包含·· -COOH、-B(0H)2、-P03H2、-R-PO3H2 及苯基，其中苯基結合一個或更多個選自下列群組取代基包含：-COOH、-b(oh)2、-po3h2 及-r-po3h2，其中 R 為一飽和或一芳香碳氫化合物；L為非發色團的單齒或多齒附屬配合基。經濟部智慧財產局員工消費合作社印製之式子分列下由係劑收接子電中點特此之明發本：在示表 :」.\J L5 yt — · 1-- ll 3 L Mu.ll M It L· 包組群列下選分部係基及代取之 --1U 位對在啶 Λ 為 A 中其! I I! I t--1ΙΙΙΙΙΙ-Ί IIIII!-I, (Please read the notes on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210 χ 297 mm) 526488 A7 B7 V. Description of the invention () Heterobenzene, 4,4, -dipyridine, 4,4'-dipyridinylethane, 4,4'-bispyridyl ethylene, 4-cyanodian, dibenzonitrile, p-diazepine Ring, No2 and acetamidine; or L may contain a coordination solvent selected from the group consisting of: acetamidine, methanol, cyanomethane, acetone, tetrahydrofuran, ethanol, dimethylformamide and dimethyloxy The sulfur-based substrate may be amorphous, microcrystalline, or semiconductor. ♦ Another feature of the present invention is that the transition metal complex contains at least one of the molecular formulas [M (NN) 2 (Y_nor-Y) (L)] n, [Μ (Ν_Ν) 2 (Υ-π〇Γ -Υ) 2] η, [M (NN) 2 (X) (Y-nor-Y) M (NN) 2 (L ^ n '[M (NNN) (Y-nor-Y) (L) 2] n '[M (NNN) 2 (Yn〇3> Y) 2 (L)] n and [M (NNN) 2 (L) 2 (Y-nor-Y) M (NNN) 2 (L) 2] n Y is selected from the group consisting of cyano, yodo, and 11-bit methylene, and nor is n-spinadiene; M is a transition metal; NN is a substituted or unsubstituted chromophoric pyrimidine complex; NR- Ν-Ν is a substituted and unsubstituted chromophore tributyral complex; L is a non-chromophore monodentate or multidentate accessory complex; X is selected from one of the following groups: Ring group and polythio ring group. Another feature of the present invention is that the transition metal complex contains at least one of the following molecular formulas: [trans-HOOCpyRun (X) 4-NC-nor-CN] 2+, {[trans- HOOCpyRun (X) 4-NC] 2-nor} 4+, [trans-CH3-OOCpyRun (X) 4-NC-nor-CN] 2+ > {[trans-CH3-OOCpyRun (X) 4-NC] 2-nor] 4+ '[trans-CH3CH2-OOCpyRuH (X) 4.NOnor-CN] 2+ and {[trans-CH3CH2-OOCpyRun (X) 4-NC] 2-nor] 4+, HOOCpy is an alien smoke Basic acid; NC-no, CN is dicyanide Spinadiene complexes; X is selected from the group consisting of polyaza macrocycles, polythio macrocycles, and NH3; trans is a structure centered on ruthenium (Ru). Another feature of the present invention is that the transition metal complex contains One molecule photosensitivity page 5 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 public love) (Please read the precautions on the back before filling out this page) # Order --------- 旅Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs r526488 ___ A7 ---------- B7___ V. Description of the invention () (Please read the precautions on the back before filling this page) The light absorption spectrum and the conduction band capable of emitting an electron into the substrate 2 are in the visible light absorption value to form an oxidized molecular photosensitizer, which has a light absorption spectrum different from that of an unoxidized molecular photosensitizer, and an electron receiving agent shows that it has A light absorption spectrum and electrons that can be received by a reduced electron acceptor have different light absorption spectra, and the charge separation between the oxidized molecular sensitizer and the reduced molecular sensitizer is maintained under continuous exposure to visible light. In this feature, the transition metal is represented by at least one of the following molecular formulas: [M (NN) 2L2] n, [M (NN) L4] n, [M (NNN) L3] n & [Μ (Ν-Ν-Ν) 2] η, M is a transition metal; NN is a polypyridine complex of a chromophore and the combination of one to two substituents selected from the group consisting of: -CO〇H, · β (0Η) 2, -POsH2 And -RP〇3h2, where r is a saturated or an aromatic hydrocarbon; NNN is a tripyridine complexing group of a chromophore selected from one of the following groups to three substituents containing · -COOH, -B (0H ) 2, -P03H2, -R-PO3H2 and phenyl, wherein the phenyl group combines one or more substituents selected from the group consisting of: -COOH, -b (oh) 2, -po3h2, and -r-po3h2, Wherein R is a saturated or an aromatic hydrocarbon; L is a non-chromophore monodentate or multidentate auxiliary complex. Under the formula printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the following is issued by the midpoint of the collection agent: ".J L5 yt — · 1-- ll 3 L Mu .ll M It L · Select the group base under the group group and replace it with the -1U position pair.

,L 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 526488 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（含：-COOH、-B(0H)2、-P〇3H2 &-R-P03H2，其中 R 為碳氫連結基；B為橋接配合基；L’可相同或不同，其係選自下列群組之一配合基包含：NC-(CH2)2-CN、NC-(CH2)3-CN、 NC-(CH2)4-CN、鹵素基、NCS-、草酸基、CO、CN·、NO、毗啶、4-氰吡啶、二苯甲腈、h2〇、〇Η·、NH3、對二氮己環、NO/、被一個或更多個甲基取代或未取代的2,2、二吡啶基及被一個或更多個甲基取代與未取代的1，丨〇-二氮雜菲；Μ ’可相同或不同，其係一過渡金屬能夠進行氧化態可逆的變化，此媒介可額外地包含一薄的透明聚合物的薄膜位於該記錄層之上。本發明之另一特點為提供一種用於儲存資料為光學可讀取形式之方法，其包含提供一光致變色金屬錯合物於一基材上，此光致變色錯合物吸收第一波長可見光；將基材及附著的光致變色錯合物浸入含有配位化合物的液體中；於選定的範圍照射附著的光致變色金屬錯合物以引發一光反應於金屬錯合物與配位化合物之間，結果反應產生一反應產物於基材上以吸收第二波長光，其第一及第二波長選用於對應二元碼作為資料儲存；移除多餘的配位化合物以使反應為不可逆的。 * 本發明之又一特點為提供一種使儲存於光學可讀取形式的資料回復之方法，其包含提供一光學資料儲存媒介包含一金屬錯合物於一基材上，此金屬錯合物以原始態及反應態存在，原始態具有一吸收或放射光譜不同於其反應態，金屬錯合物於原始態之範圍對應一二元數值丨或〇，第7頁 (請先閱讀背面之注意事項再填寫本頁) ---------tr----------^ 526488 A7 五、發明說明（) 而金屬錯合物於反應態之範圍對應為相反的二元數值；將媒介暴露於一光束中’此光具有一波長可選擇性地被原始態金屬錯合物或反應態金屬錯合物所吸收；以及於媒介曝光後偵測該光束強度，被傳送的光束強度顯示該光束係暴露於原始金屬錯合物的範圍或反應態金屬錯合物的範圍，因此而將儲存於記錄媒介的二元數值回復。· 本發明之又一特點為提供一種用於儲存資料為光學可讀取形式之方法’其包含提供一光學資料記綠媒介包含一基材構成一非同分異構的金屬錯合物支撐區域，此非同分異構的金屬錯合物區域具有第一吸收光譜對應一二元數值1或0 ;將非同分異構的金屬錯合物暴露於uv至可見光範圍的電磁放射線中，因而造成非同分異構的金屬錯合物轉變成同分異構的金屬錯合物區域，此同分異構的金屬錯合物具有第二吸收光譜不同於該第一吸收光譜，此第二吸收光譜對應於相反的二元數值，更特別地是，此基材可選自二氧化鶴、二氧化鈦、二氧化鋅及二氧化錫，此基材亦可為微結晶的或包含微粒懸浮形式，此微粒具有平均直徑範圍約10 nm至約50 nm。本發明之另一特點為提供一種用於儲存資料為光學可讀取形式之方法’其包含提供—未氧化的分子感光劑及一未還原的電子接收劑附著於一寬能隙的半導體基材，此未氧化的分子感光劑吸收第一波長可見光，此未還原的電子接收劑吸收第二波長可見光；以及於選定的範圍照射未氧化的分子感光劑以引發一電子射入空的基材導電帶，接第8頁本紙張尺度適用中國國家標準（CNS)A4規^7^_297公爱） I — I I I I I I I I * I I I I I I I ^ ·1111111« (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 526488 五、發明說明（著由電子接收劑接收該電子，因而形成一氧化的分子咸> 愁光劑，此氧化的分子感光劑吸收第三波長的光並形成還原、白勺電子接收劑，此還原的電子接收劑吸收第四波長的光，第三及第四波長組合被選用於對應二元碼作為資料儲存。本發明之另一特點為提供一種使儲存於光學可讀取形式的資料回復之方法，其包含提供一光學資料儲存媒介包含一分子感光劑及一電子接收劑吸收於一寬能隙的半導體基材上，其中此媒介的一個或更多個區域為氧化的分子感光劑或還原的電子接收劑，此氧化的分子感光劑具有一吸收或放射光譜不同於未氧化形式的分子感光劑的光譜，此還原的電子接收劑具有一吸收或放射光譜不同於未還原的電子接收劑的光譜，此氧化分子感光劑的範圍與還原電子接收劑的範圍對應於二元數值1或0，且分子感光劑未氧化態的範圍與還原電子接收劑未還原態的範圍對應於相反的二元數值。在此特點中分子感光劑以下列至少一分子式表示· [M(N-N)2L2]n、[M(N-N)L4]n、[M(N-N-N)L3]n 及[Μ(Ν-Ν-Ν)2]η，Μ 為一過渡金屬具有氧化態；Ν-Ν為發色團的聚吡啶配合基具有一電荷及結合選自下列群組之一至二個取代基包含：-COOH、-Β(〇Η)2、-Ρ〇3Η2 及-R-P03H2，其中 R 為一飽和或一芳香碳氫化合物；N-N-N為發色團的三”比症配合基具有一電荷及結合選自下列群組之一至三個取代基包含·· -COOH、-B(OH)2、-P〇3H2、-R-P03H2 及苯基，其中第9頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）丨 ----丨丨丨丨--- -----訂--------·線.411^ ί請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 _____ B7 _ 五、發明說明（）苯基結合一個或更多個選自下列群組取代基包含：-COOH、-B(0H)2、-P〇3H2 及-r_p〇3h2，其中 R 為一飽和或一芳香碳氫化合物；L為非發色團的單齒或多齒附屬配合基具有一電荷；且η為總電荷數包含μ氧化態及配合基電荷的代數總和。此方法更包含反射一光束偏離該媒介，此光束具有一波長選擇性地被氧化分子感光劑或未氧化態分子感光劑所吸收；以及被媒介反射之後偵測光束強度，此被反射的光束強度顯示該光束係穿透氧化分子感光劑與還原電子接收劑的範圍或未氧化態分子感光劑與未還原態電子接收劑的範圍，因而將儲存於記錄媒介的二元數值回復。本發明之另一特點為提供一金屬錯合物以下列分子式之一表示：[(4,4’-HP〇3CH2)2bpyRu(CN)4]4· 、[(4,4，- HP03)2bpyRu(CN)4 广、（4,4，-HP03CH2)2(bpy)Re(C0)3(X)、 [(dcbH2)Ru(CN)4]4-及(4,4’-HP03)2 (bpy)Re(CO)3(X);其中 X 係選自 CN·、NCS、NC-(CH2)2-CN ' NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、CO、NO、吡啶、4-氰吡啶、二苯甲晴、H20、 NH3 及 NO2、本發明之又一特點為提供一光學資料記錄媒介包含一記錄層及一基材，此基材包含一寬能隙半導體，記錄層包含一電子接收劑及一分子感光劑，此分子感光劑又下列分子式之一表示：[(4,4’-HP03CH2)2bpyRu(CN)4]4·、[(4,4，-HP03)2bpyRu(CN)4]4· 、（4,4，-HP03CH2)2(bpy)Re(C0)3(X) 、 [(dcbH2)Ru(CN)4]4·及(4,4’-HP03)2 (bpy)Re(CO)3(X);其中 X 係選第10頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------------41^--------訂---------旅 (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製五、發明說明（）自 CN_、NCS、NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、CO、NO、吡啶、4-氰吡啶、二苯甲晴、H20、 N Η 3及N 0 2-。此分子感光劑具有一光吸收光譜及能夠射入一電子至基材空的導電帶在可見光吸收值之上，以形成具有不同光吸收光譜的氧化分子感光劑，此電子接收劑具有一光吸收光譜及能夠接收電子，以形成具有不同光吸收光譜的還原電子接收劑’以及氧化分子感光劑與還原電子接收劑之間電荷分離係維持在持續照射可見光。在本發明之此特點中，電子接收劑係由下列分子式之一表示： A7 B7, L This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 526488 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (including: -COOH, -B (0H) 2 , -P〇3H2 & -R-P03H2, where R is a hydrocarbon linking group; B is a bridging complex; L 'may be the same or different, and is selected from one of the following groups. The complex includes: NC- (CH2 ) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halo, NCS-, oxalate, CO, CN, NO, pyridine, 4-cyanopyridine, benzoyl Nitrile, h2〇, 〇 ··, NH3, p-diazepine, NO /, 2,2 or dipyridyl substituted or unsubstituted with one or more methyl groups, and substituted with one or more methyl groups It can be the same as or different from the unsubstituted 1, 丨 -diazaphenanthrene; M ', which is a transition metal capable of reversibly changing the oxidation state. This medium can additionally include a thin transparent polymer film located in the On the recording layer. Another feature of the present invention is to provide a method for storing data in an optically readable form, which includes providing a photochromic metal complex. The photochromic complex on a substrate absorbs visible light at a first wavelength; the substrate and the attached photochromic complex are immersed in a liquid containing a complex compound; and the attached photochromic is irradiated in a selected range The metal complex compound initiates a photoreaction between the metal complex compound and the coordination compound. As a result, the reaction produces a reaction product on the substrate to absorb light of a second wavelength, and the first and second wavelengths are selected for the corresponding binary Codes are stored as data; excess coordination compounds are removed to make the reaction irreversible. * Another feature of the present invention is to provide a method for recovering data stored in an optically readable form, which includes providing an optical data storage The medium includes a metal complex on a substrate. The metal complex exists in a raw state and a reactive state. The raw state has an absorption or emission spectrum different from the reactive state. The metal complex corresponds to the range of the raw state. One binary value 丨 or 〇, page 7 (please read the notes on the back before filling this page) --------- tr ---------- ^ 526488 A7 V. Invention Description () and metal complex The range of reactive states corresponds to opposite binary values; exposing the medium to a light beam 'This light has a wavelength that can be selectively absorbed by the original metal complex or the reactive metal complex; and exposure to the medium After detecting the intensity of the beam, the transmitted beam intensity shows that the beam is exposed to the range of the original metal complex or the range of the reactive metal complex, so the binary value stored in the recording medium is restored. · 本Another feature of the invention is to provide a method for storing data in an optically readable form, which includes providing an optical data recording medium comprising a substrate comprising a non-isomeric metal complex support region. The non-isomeric metal complex region has a first absorption spectrum corresponding to a binary value of 1 or 0; the non-isomeric metal complex is exposed to electromagnetic radiation in the UV to visible light range, thereby causing non-isomeric metal complexes The isomerized metal complex is converted into an isomerized metal complex region. This isomerized metal complex has a second absorption spectrum different from the first absorption spectrum. The second absorption spectrum corresponds to the opposite binary value. More specifically, the substrate may be selected from the group consisting of crane dioxide, titanium dioxide, zinc dioxide, and tin dioxide. The substrate may also be microcrystalline or contain fine particles. In suspended form, this particle has an average diameter ranging from about 10 nm to about 50 nm. Another feature of the present invention is to provide a method for storing data in an optically readable form, which includes providing-an unoxidized molecular photosensitizer and an unreduced electron acceptor attached to a semiconductor substrate with a wide energy gap. The non-oxidized molecular photosensitizer absorbs visible light at a first wavelength, and the non-reduced electron acceptor absorbs visible light at a second wavelength; and irradiates the non-oxidized molecular photosensitizer in a selected range to cause an electron to be injected into the empty substrate to conduct electricity Belt, continued on page 8. This paper size applies Chinese National Standard (CNS) A4 regulations ^ 7 ^ _297 public love) I — IIIIIIII * IIIIIII ^ · 1111111 «(Please read the precautions on the back before filling this page) Wisdom of the Ministry of Economic Affairs Printed by the Consumer Affairs Cooperative of the Property Bureau 526488 V. Description of the Invention (The electron is received by the electron receiving agent, thus forming an oxidized molecular salt> A gloomy agent, this oxidized molecular photosensitizer absorbs light of a third wavelength and forms a reduction And electron receiver, the reduced electron receiver absorbs light of the fourth wavelength, and the combination of the third and fourth wavelengths is selected to correspond to the binary code As data storage. Another feature of the present invention is to provide a method for recovering data stored in an optically readable form, which includes providing an optical data storage medium including a molecular photosensitizer and an electron receiving agent absorbed in a wide energy On a semi-conducting semiconductor substrate, one or more regions of the medium are oxidized molecular photosensitizers or reduced electron acceptors. The oxidized molecular photosensitizers have a molecular photosensitivity that is different from that of the unoxidized form. The spectrum of the reduced electron acceptor has an absorption or emission spectrum different from that of the unreduced electron acceptor. The range of the oxidized molecular photosensitizer and the range of the reduced electron acceptor correspond to binary values of 1 or 0. And the range of the molecular sensitizer's unoxidized state and the range of the reduced electron receiver's unreduced state correspond to opposite binary values. In this feature, the molecular sensitizer is expressed by at least one of the following molecular formulas: [M (NN) 2L2] n, [M (NN) L4] n, [M (NNN) L3] n and [M (Ν-Ν-Ν) 2] η, where M is a transition metal with an oxidation state; N-N is a polypyridine with a chromophore Cooperate Has one charge and is bonded to one or two substituents selected from the group consisting of: -COOH, -B (〇Η) 2, -PO3Η2, and -R-P03H2, where R is a saturated or an aromatic hydrocarbon ; NNN is a chromophore with a three- "syndrome complex having one charge and binding selected from one to three substituents of the group consisting of -COOH, -B (OH) 2, -P〇3H2, -R- P03H2 and phenyl, of which the paper size on page 9 is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 丨 ---- 丨丨丨丨 --- ----- Order ---- ---- · line. 411 ^ Please read the notes on the back before filling out this page) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____ B7 _ 5. Description of the invention () Phenyl combined with one or more Substituents selected from the group consisting of: -COOH, -B (0H) 2, -P03H2, and -r_p〇3h2, where R is a saturated or an aromatic hydrocarbon; L is a non-chromophore monomer The dentate or multidentate accessory ligand has a charge; and η is the algebraic sum of the total charge number including the μ oxidation state and the charge of the ligand. The method further includes reflecting a light beam deviating from the medium, the light beam having a wavelength selectively absorbed by the oxidized molecular photosensitizer or the non-oxidized molecular photosensitizer; and detecting the intensity of the light beam after being reflected by the medium, and the intensity of the reflected light beam It is shown that the light beam penetrates the range of the oxidized molecular photoreceptor and the reduced electron acceptor or the range of the non-oxidized molecular photoreceptor and the unreduced electron acceptor, and thus restores the binary value stored in the recording medium. Another feature of the present invention is to provide a metal complex represented by one of the following molecular formulas: [(4,4'-HP〇3CH2) 2bpyRu (CN) 4] 4 ·, [(4,4,-HP03) 2bpyRu (CN) 4 Cantonese, (4,4, -HP03CH2) 2 (bpy) Re (C0) 3 (X), [(dcbH2) Ru (CN) 4] 4- and (4,4'-HP03) 2 ( bpy) Re (CO) 3 (X); where X is selected from CN, NCS, NC- (CH2) 2-CN 'NC- (CH2) 3-CN, NC- (CH2) 4-CN, halo , CO, NO, pyridine, 4-cyanopyridine, dibenzophenone, H20, NH3, and NO2. Another feature of the present invention is to provide an optical data recording medium including a recording layer and a substrate. The substrate includes a For a wide band gap semiconductor, the recording layer includes an electron acceptor and a molecular photosensitizer, and this molecular photosensitizer is represented by one of the following molecular formulas: [(4,4'-HP03CH2) 2bpyRu (CN) 4] 4, [(4 , 4, -HP03) 2bpyRu (CN) 4] 4, (4,4, -HP03CH2) 2 (bpy) Re (C0) 3 (X), [(dcbH2) Ru (CN) 4] 4, and ( 4,4'-HP03) 2 (bpy) Re (CO) 3 (X); of which X is selected on page 10. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ---- -------- 41 ^ -------- Order --------- Travel (please read the notes on the back before filling this page) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention () From CN_, NCS, NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halogen Radical, CO, NO, pyridine, 4-cyanopyridine, dibenzophenone, H20, N Η 3 and N 0 2-. The molecular photosensitizer has a light absorption spectrum and can pass an electron to the substrate. The conductive band is above the visible light absorption value to form oxidized molecular photosensitizers with different light absorption spectra. The electron receiving agent has a light absorption. The spectrum and the ability to receive electrons to form a reduced electron acceptor 'with different light absorption spectra and the charge separation between the oxidized molecular photosensitizer and the reduced electron acceptor are maintained under continuous exposure to visible light. In this feature of the invention, the electron receiving agent is represented by one of the following molecular formulas: A7 B7

其中 Α為说啶在對位之取代基係部分選自下列群組包含：-COOH、-B(OH)2、-P〇3H2 及-R-P〇3H2，其中 R 為碳氫連結基；B為橋接配合基；L’可相同或不同，其係選自下列群組之一配合基包含·· NC-(CH2)2-CN、NC-(CH2)3-CN、 NC-(CH2)4-CN、鹵素基、NCS.、草酸基、CO、CN-、NO、吡啶、4-氰毗啶、二苯甲腈、HzO、〇Η·、NH3、對二氮己環、NO,、被一個或更多個甲基取代或未取代的2,2’·二吡啶基及被一個或更多個甲基取代與未取代的1，1 〇-二氮雜菲；M，可相同或不同，其係一過渡金屬能夠進行氧化態可逆的變化，此媒介可額外地包含一薄的透明聚合物的薄膜位於該記錄層之上。第11頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------^ IAW,% (請先閱讀背面之注意事項再填寫本頁) 526488 Α7 Β7 經濟部智慧財產咼811 五、發明說明（圖式簡單說明：第 la 圖顯示 Ru(dcH2b)2(COO)2 在 Zr02/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用後之光譜。第 lb 圖顯示 Ru(dcH2b)2(COO)2 在 Ti02/CH3CN ♦上之原始光譜’以及在大於400 nm波長下光解作用後之光譜。第2a圖顯示Ru(cicH2b)2(Cl)2在Zr02/CH3CN上之原始光譜，以及在大於400 nm波長下光解作用後之光譜。第2b圖顯示Ru(dcH2b)2(Cl)2在Ti02/CH3CN上之原始光譜，以及在大於400 nm波長下光解作用後之光譜。第 3a 圖顯示 Ru(dCH2b)2(NCS)2 在 Zr02/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用後之光第 3b 圖顯示 Ru(dcH2b)2(NCS)2 在 Ti02/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用後之光譜。第 4a 圖顯示 Fe[terpy(COOH)3]2(Cl〇4)2 在 Zr02/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用後之光譜。第 4b 圖顯示 Fe[tei:py(C00H)3]2(C104)2 在 Ti〇2/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用後之光譜。第12頁 ΐ 家標^ (CNS)A4 規格（210 X 297 公ϋ 两 ------ 訂-----—I hUk-------1--------------- {請先閱讀背面之注音？事項再填寫本頁)Wherein A is the substituent group of the pyridine in the para position selected from the group consisting of: -COOH, -B (OH) 2, -P03H2, and -RP〇3H2, where R is a hydrocarbon linking group; B is Bridging complex; L 'can be the same or different, and it is selected from one of the following groups. The complex includes: NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4- CN, halogen, NCS., Oxalate, CO, CN-, NO, pyridine, 4-cyanopyridine, dibenzonitrile, HzO, 〇 ··, NH3, p-diazepine, NO, Or more methyl substituted or unsubstituted 2,2′-dipyridyl and substituted with one or more methyl and unsubstituted 1,10-diazaphenanthrene; M, may be the same or different, It is a transition metal capable of reversibly changing the oxidation state, and the medium may additionally include a thin transparent polymer film on the recording layer. Page 11 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------------------- Order ------- -^ IAW,% (Please read the notes on the back before filling this page) 526488 Α7 Β7 Intellectual Property of the Ministry of Economic Affairs 811 V. Description of the invention (Simplified illustration of the diagram: Figure la shows Ru (dcH2b) 2 (COO) 2 The original spectrum on Zr02 / CH3CN, and the spectrum after photolysis at a wavelength greater than 400 nm. Figure lb shows the original spectrum of Ru (dcH2b) 2 (COO) 2 on Ti02 / CH3CN ', and Spectrum after photolysis at 400 nm. Figure 2a shows the original spectrum of Ru (cicH2b) 2 (Cl) 2 on Zr02 / CH3CN and the spectrum after photolysis at wavelengths greater than 400 nm. Figure 2b The original spectrum of Ru (dcH2b) 2 (Cl) 2 on Ti02 / CH3CN and the spectrum after photolysis at wavelengths greater than 400 nm are shown. Figure 3a shows Ru (dCH2b) 2 (NCS) 2 at Zr02 / CH3CN The original spectrum above, and the light after photolysis at wavelengths greater than 400 nm. Figure 3b shows the original spectrum of Ru (dcH2b) 2 (NCS) 2 on Ti02 / CH3CN, and light at wavelengths greater than 400 nm. Spectrum after action. Figure 4a shows the original spectrum of Fe [terpy (COOH) 3] 2 (Cl〇4) 2 on Zr02 / CH3CN, and the spectrum after photolysis at a wavelength greater than 400 nm. Figure 4b Shows the original spectrum of Fe [tei: py (C00H) 3] 2 (C104) 2 on Ti〇2 / CH3CN and the spectrum after photolysis at wavelengths greater than 400 nm. Page 12 ΐ Housemark ^ (CNS ) A4 specifications (210 X 297 public ϋ two ------ order ------I hUk ------- 1 --------------- {Please Read the Zhuyin on the back? Matters before filling out this page)

526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）第5圖說明Type I裝置包含Ru(dcH2b)2(L)2錯合物在氰甲烷存在下進行光反應之作用式。第 6 圖說明 Type I 裝置包含[Fe(trpy)(C00H)3](C104)2 錯合物在氰甲烷存在下進行光反應之作用式。第7a圖顯示Ru(dcH2b)2(COO)2在Zr02/Ar上之原始光譜，以及在大於500 nm波長下光解作用.6小時後之光譜。第 7b 圖顯示 Ru(dcH2b)2(COO)2 在 Zr02/CH3CN 上之原始光譜，以及在大於500 nm波長下光解作用丨，2, 3, 4，5，及6小時後之光譜。第 7c 圖顯示 Ru(dcH2b)2(COO)2 在 Zr02/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用15，3〇及4 5分鐘後之光譜。第8a圖顯示Ru(dcH2b)2(Cl)2在Zr02/Ar上之原始光譜，以及在大於500 nm波長下光解作用6小時後之光譜。第8b圖顯示Ru(dcH2b)2(Cl)2在Zr02/CH3CN上之原始光譜，以及在大於500 nm波長下光解作用丨，2, 3, 5, 及6小時後之光譜。第8c圖顯示Ru(dcH2b)2(Cl)2在Zr02/CH3CN上之原始光譜，以及在大於400 nm波長下光解作用15,30,45 及60分鐘後之光譜。第9a圖顯示Ru(dcH2b)2(NCS)2在Zr02/Ar上之原始光譜，以及在大於500 nm波長下光解作用6小時後之光第13頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------J-------變--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）譜。第 9b 圖顯示 Ru(dcH2b)2(NCS)2 在 Zr02/CH3CN 上之原始光譜，以及在大於500 nm波長下光解作用丨，2及 3小時後之光譜。第 9c 圖顯示 Ru(dcH2b)2(NCS)2 在 Zr〇2/CH3CN 上之原始光譜，以及在大於400 nm波長下光解作用4丨5及30 分鐘後之光譜。第10圖顯示1^((1(：1121))2(>^3)2在乙1：〇2/(：113€1^/5?7上之原始光譜，以及在大於400 nm波長下光解作用5, 10, 15, 20, 25及30分鐘後之光譜。第 11a 圖顯示觀察[Ru(dcH2b)2(NCCH3)2]2 + (光譜 A)在 Zr02 薄膜上浸泡於含有0.1M氯化四丁基銨（TBAC1)的甲醇溶液中，以未過濾150 W氙（Xe)燈照射該薄膜之前與之後的光譜變化。第1 lb圖顯示觀察[Ru(dcH2b)2(NCCH3)2]24*錯合物在含有 0.1 M TBAC1的甲醇溶液中，以雷射激發之前與之後的光譜變化。第 12 圖顯示[HOOCpyRiANHA-NC-nor-CN-RuWNHApy COOH]4+在甲醇溶液中之原始光譜，利用截土波長 5 40 nm的150瓦氙（Xe)燈光解作用5、1〇及20 /刀鐘後之光譜，以及沒有截止波長下光解作用2 ' 5 及1 0分鐘後之光譜。第 13 圖顯示[HOOCpyRu n(NH3)4-NC-nor-CN-Run(NH3)4py COOH]4+分散在4-聚乙婦毗啶/10%苯乙烯透明的第14頁 _^ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —丨丨丨—丨—i丨丨丨—丨訂ί——I (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）態聚合物基板中之原始吸收光譜，利用截止波長 540nm下照射5、15、25及45分鐘後之吸收光谱’ 以及沒有截止波長下照射5分鐘後之吸收光譜。第14圖說明Type II裝置之作用式，其中正疲二烯被異構化為四環婦。第15圖說明Type III裝置之作用式，其包含一分子感光劑及電子接收劑吸附在二氧化鈦基材上。第 16 圖顯示[Ru(dcbH2)2(bpy)2]2+ 與雙核的 K[trans-HOOCpyRu'NHA-NCRu^CNh]錯合物吸附在透明的一氧化鈥薄膜上之原始光譜，以及以i 5〇 w氙（Xe) 燈光解作用5、1 0及20秒後之光譜。發明詳細說明：以下詳細說明與範例顯示本發明之較佳實施例，熟習該項技術者於瞭解本發明之後，在不脫離本發明之精神範圍内，當可作些許更動满飾及等同之變化替換，因此，本發明以較佳實施例說明如上’不應視為限定本發明之範圍。簡介，於較佳實施例中，三種不同形式的公名# ^ 、曰1 77子能階資料儲存系統被預期’其皆是透過使用有機金屬的過度金屬錯合物運作，這些物種將系統特性分為Type I、n u、及πι，其具有共同的特性為強烈的金屬對配合基雷共Μ 何轉移（metal-to ligand charge transfer，MLCT)吸收帶用以, J以支配可見光（例第15頁 ------iif------- 丨訂---------嫌 (請先閱讀背面之注意事項再填寫本頁) 526488526488 Printed by A7 B7, Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs 5. Description of the invention () Figure 5 illustrates that the Type I device contains Ru (dcH2b) 2 (L) 2 complex in the presence of cyanogen methane. . Figure 6 illustrates the action formula of a Type I device containing [Fe (trpy) (C00H) 3] (C104) 2 complex in the presence of cyanomethane.) Figure 7a shows the original spectrum of Ru (dcH2b) 2 (COO) 2 on Zr02 / Ar, and its photolysis at a wavelength greater than 500 nm. The spectrum after 6 hours. Figure 7b shows the original spectrum of Ru (dcH2b) 2 (COO) 2 on Zr02 / CH3CN and the photolysis at wavelengths greater than 500 nm, 2, 3, 4, 5, and 6 hours later. Figure 7c shows the original spectra of Ru (dcH2b) 2 (COO) 2 on Zr02 / CH3CN, and the spectra after 15, 30, and 45 minutes of photolysis at wavelengths greater than 400 nm. Figure 8a shows the original spectrum of Ru (dcH2b) 2 (Cl) 2 on Zr02 / Ar, and the spectrum after 6 hours of photolysis at a wavelength greater than 500 nm. Figure 8b shows the original spectrum of Ru (dcH2b) 2 (Cl) 2 on Zr02 / CH3CN and the photolysis at wavelengths greater than 500 nm, 2, 3, 5, and 6 hours later. Figure 8c shows the original spectrum of Ru (dcH2b) 2 (Cl) 2 on Zr02 / CH3CN, and the spectrum after 15, 30, 45 and 60 minutes of photolysis at wavelengths greater than 400 nm. Figure 9a shows the original spectrum of Ru (dcH2b) 2 (NCS) 2 on Zr02 / Ar, and the light after 6 hours of photolysis at a wavelength greater than 500 nm. Page 13 This paper applies Chinese National Standards (CNS) A4 specification (210 X 297 mm) ------- J ------- change -------- order --------- line (please read the first Note for this page, please fill in this page) 526488 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 9b shows the original spectrum of Ru (dcH2b) 2 (NCS) 2 on Zr02 / CH3CN, and the photolysis at wavelengths greater than 500 nm, 2 and 3 hours later. Figure 9c shows the original spectrum of Ru (dcH2b) 2 (NCS) 2 on Zr〇2 / CH3CN, and the spectrum after photolysis at wavelengths greater than 400 nm for 4 5 and 30 minutes. Figure 10 shows the original spectrum of 1 ^ ((1 (: 1121)) 2 (> ^ 3) 2 on B 1: 〇2 / (: 113 € 1 ^ / 5? 7, and at wavelengths greater than 400 nm Spectra after 5, 10, 15, 20, 25 and 30 minutes of photolysis. Figure 11a shows the observations of [Ru (dcH2b) 2 (NCCH3) 2] 2 + (spectrum A) immersed in Zr02 film containing 0.1 Spectral changes before and after irradiating the film with an unfiltered 150 W xenon (Xe) lamp in a methanol solution of M tetrabutylammonium chloride (TBAC1). Figure 1 lb shows observations [Ru (dcH2b) 2 (NCCH3) 2] 24 * complex in a methanol solution containing 0.1 M TBAC1 before and after laser excitation. Figure 12 shows [HOOCpyRiANHA-NC-nor-CN-RuWNHApy COOH] 4+ in a methanol solution. The original spectra were obtained using 150 Watt Xenon (Xe) light with a cut-off wavelength of 5 40 nm, spectra after 5, 10, and 20 / knife, and photosynthesis without cut-off wavelengths after 2 '5 and 10 minutes. Figure 13 shows [HOOCpyRu n (NH3) 4-NC-nor-CN-Run (NH3) 4py COOH] 4+ dispersed in 4-polyethoxypyrimidine / 10% styrene transparent page 14_ ^ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Li) — 丨丨丨 — 丨 —i 丨丨丨 — 丨 Order ί——I (Please read the notes on the back before filling this page) 526488 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention The original absorption spectrum in the () polymer substrate is based on the absorption spectrum after 5, 15, 25, and 45 minutes of irradiation at a cut-off wavelength of 540 nm, and the absorption spectrum after 5 minutes of irradiation without a cut-off wavelength. Figure 14 illustrates Type II The working formula of the device, in which isadiene is isomerized into tetracycline. Figure 15 illustrates the working formula of the Type III device, which contains a molecule of a photosensitizer and an electron acceptor adsorbed on a titanium dioxide substrate. Figure 16 The original spectrum of [Ru (dcbH2) 2 (bpy) 2] 2+ and dinuclear K [trans-HOOCpyRu'NHA-NCRu ^ CNh] complex adsorbed on a transparent monoxide 'film, and i 5〇 w Xenon (Xe) light spectrum after 5, 10, and 20 seconds of solution effect. Detailed description of the invention: The following detailed description and examples show the preferred embodiments of the present invention. Without departing from the spirit of the invention, Some modifications and equivalent changes are replaced. Therefore, the present invention is described in the preferred embodiment as described above and should not be regarded as limiting the scope of the present invention. In brief, in the preferred embodiment, three different forms of the common name # ^, said the 77 sub-level data storage system are expected to 'all operate through the use of organometallic metametal complexes, these species will have system characteristics Divided into Type I, nu, and π, which have a common characteristic is that a strong metal-to-ligate charge transfer (MLCT) absorption band is used, and J is used to control visible light (Example 15 Page ------ iif ------- 丨 Order --------- Suspect (Please read the precautions on the back before filling this page) 526488

經濟部智慧財產局員工消費合作社印製 i、發明說明（）如波長範圍在400及800 nm之間），以及在uv範圍中（例如波長範圍在200及400 nm之間）強烈的配合基中心 (ligand centered，LC)轉移，紫外線或可見光激發促進該等分子物種進入上層電子激發態，當與相同分子之基態比較時，此種激發態之分子物種可顯示一特殊的反應性。以下揭露不同種類的過渡金屬錯合物，當被涸定於透明的固體基材上或是包含於聚合物的基板中_，其能夠進行分子能階光化學反應產生可見光範圍的顏色變化或改變該等分子物種的放射特性，伴隨分子組成或電子結構的改變，永久的顏色變化係藉由以UV-可見光照射而產生且可在傳輸中被讀取，伴隨以光引發分子组成或電子結構的改變，放射特性的永久變化可藉由監測來自激發的分子物種所放射的光在任何方向被讀取。Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the invention description (such as the wavelength range between 400 and 800 nm), and the strong base center in the UV range (for example, between 200 and 400 nm) (ligand centered, LC) transfer, UV or visible light excitation promotes these molecular species to enter the upper electronic excited state. When compared with the ground state of the same molecule, this excited molecular species can show a special reactivity. The following discloses that different types of transition metal complexes, when fixed on a transparent solid substrate or contained in a polymer substrate, can perform molecular energy-level photochemical reactions to produce color changes or changes in the visible light range. The radiation characteristics of these molecular species are accompanied by changes in molecular composition or electronic structure. Permanent color changes are generated by irradiation with UV-visible light and can be read during transmission. With the initiation of molecular composition or electronic structure by light Alterations, permanent changes in emission characteristics can be read in any direction by monitoring light emitted from excited molecular species.

Type I系統Type I system

Type I系統通常包含一薄膜例如具有吸收光反應金屬錯合物之膠體半導體或非晶矽，將此薄膜浸入一配位溶劑或含有配位配合基的溶液中，藉由適當波長的光激發提升金屬錯合物進入電子激發態其反應性用於配合基取代反應，激發態金屬錯合物可與配位溶劑或溶於適當溶劑的配位配合基反應，兩種狀況之反應產物為新的分子其顏色或放射特性不同於原來的金屬錯合物。於Type I系統之一較佳實施例中，溶劑為反應性物種之攜帶劑，此反應性物種與金屬錯合物反應因而改變顏色或放射特性，本實施例之此兩種變化可被想像為：（i)若金第16頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ------^----；----------訂---------線 (請先8a讀背面Μ涑意事頊再填寫本經濟部智慧財產局員工消費合作社印製 526488 五、發明說明（屬錯合物吸附在固體基材上發光，此反應性物種可選自那些可與激發態金屬錯合物反應以抑制放射之物種；或者（ii) 若金屬錯合物吸附在固體基材上照射而未發光，則此反應性物種可選自那些可與激發態金屬錯合物反應以形成新的物種，當以適當波長照射此新的物種會發光，任何一種變化，反應造成一分子吸收或發出與未反應金屬錯合物不同波長的光，光吸收與光放射（例如顏色差異）之差異可作為儲存資料之方法，藉由指定一個二元碼數值（〇或1)為原始態，而留下的二元碼數值（〇或1}為反應態。於一實施例中，Type I系統包含一透明微結晶或非晶形金屬氧化物薄膜，其係以一金屬錯合物作用屬於具有二個配位數的過渡金屬聚毗啶錯合物之特定至螭廷些金屬錯合物以下列分子式表示： [M(N-N)2L2]n [M(N-N)L4]n [M(N-N-N)L3]n [M(N-N-N)2]n 其中n為錯合物總電荷數，非特別指定，為金屬中、、氧化態數及配合基電荷的代數總和，Μ為一過渡金屬包本鐵、鉛、錄、銅、銀、飽、銘、鍊、鐵、釕或接叫％，但最佳為鐵或釕。Ν-Ν為發色團的聚吡啶配合基，例如 4 Ί '二 ΤΤ比咬結合下列群組之一或二個取代基包含·· 、 Β(ΟΗ)2、-Ρ〇3Η2 或-R-P〇3H 2(其中 R 為一飽和哎——4 产〜方香碳氫官能基，例如亞甲基、乙基、丙基等，或是苯基）· 1 1〇第17頁 K紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公髮） (請先閱讀背面之注意事項再填寫本頁)Type I systems usually include a thin film, such as a colloidal semiconductor or amorphous silicon with a metal complex that absorbs light. This film is immersed in a coordination solvent or a solution containing a coordination complex, and lifted by light with an appropriate wavelength. The metal complex enters the electronic excited state and its reactivity is used for the substitution reaction of the ligand. The excited metal complex can react with a coordination solvent or a coordination complex dissolved in an appropriate solvent. The reaction product of the two conditions is new. The molecule has a different color or emission characteristic than the original metal complex. In a preferred embodiment of the Type I system, the solvent is a carrier of a reactive species, and the reactive species reacts with the metal complex to change the color or radiation characteristics. The two changes in this embodiment can be imagined as : (I) Ruojin page 16 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------ ^ ----; ---------- Order --------- line (please read 8M on the back of the book first, and then fill in the printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 526488 V. Description of the invention (It is a complex compound adsorbed on a solid substrate The reactive species may be selected from those species that can react with excited metal complexes to suppress radiation; or (ii) if the metal complexes are adsorbed on a solid substrate and irradiated without emitting light, the reactive species The species can be selected from those that can react with the excited metal complex to form a new species. When this new species is illuminated at an appropriate wavelength, it will emit light. Any change, the reaction causes a molecule to absorb or emit with the unreacted metal complex Different wavelengths of light, differences in light absorption and light emission (such as color differences) It can be used as a method for storing data by specifying a binary code value (0 or 1) as the original state and leaving the binary code value (0 or 1) as the reactive state. In one embodiment, the Type I system It contains a transparent microcrystalline or amorphous metal oxide thin film, which acts as a metal complex and belongs to the transition metal polypyridine complex with two coordination numbers. Molecular formula: [M (NN) 2L2] n [M (NN) L4] n [M (NNN) L3] n [M (NNN) 2] n where n is the total charge number of the complex, which is not specifically specified, is The algebraic sum of the number of oxidation states and the charge of the complex in the metal, M is a transition metal including iron, lead, copper, copper, silver, saturated, chain, iron, ruthenium, or nickel, but the best is Iron or ruthenium. N-N is a polypyridine complex of a chromophore, for example, 4 Ί 'di TTT ratios are combined with one or two of the following groups containing ··, Β (〇Η) 2, -PO3Η2 Or -RP〇3H 2 (where R is a saturated hey-4 produced ~ square aromatic hydrocarbon functional groups, such as methylene, ethyl, propyl, etc., or phenyl) · 1 10 page 17 K paper size applies to China National Standard (CNS) A4 specifications (210 X 297) (please read the precautions on the back before filling this page)

I I I II II ^ « — — — — — — I 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）一氮雜菲由下列一或二個取代基所取代：-⑶^^、. b(oh)2、-po3h2 或-R-P〇3H 2(其中 R 如上述定義）；2 2、一啥淋由下列一或二個取代基所取代：_c〇〇H、·β(〇η)2、 -ΡΟ#2或-R-PChH 2(其中R如上述定義），當超過一個Ν_ Ν基出現在化合物中時（例如（Ν-Ν)2)，這些ν_ν基可相同或不同。Ν-Ν-Ν為發色團的三吡啶配合基結合選自•下列群組之一、二或三個取代基包含：-C〇〇H、_Β(〇η)2、·ρ〇3η2 或-R-PChH2(其中R如上述定義），或被苯基所取代，其中苯基結合下列取代基包含：_COOH、-B(OH)2、-P〇3H2或 -R-P〇3H2(其中R如上述定義），較佳的取代基在對位（para position)，當超過一個N-N-N基出現在化合物中時（例如 (N-N-N)2)，這些N-N-N基可相同或不同。l獨自地為非發色團的單齒或多齒附屬配合基，例如NC-(CH2)2-CN、NC- (CH2)3-CN、NC-(CH2)4-CN、鹵素基、NCS_、N3-、_CH3-、Η·、草酸基、CO、CN·、NO、H20、OH.、NH3、***、吡啶、對二氮雜苯、4,4’-二p比咬、4,4’-二说淀基乙貌、4,4’-二p比啶基乙晞、4-氰毗啶、二苯甲腈、對二氮己環、N03-或乙酿丙酮；或者L為一配位溶劑例如：乙醯丙酮、甲醇、氰甲烷、丙酮、四氫呋喃、乙醇、二甲基甲醯胺或二甲基氧硫基。此類錯合物之成員可依據已發表於文獻之方法製備 (例如，R. Argazzi，C.A. Bignozzi，T.A. Heimer，P.Castellano, G.J. Meyer Inorg. Chem. 33? 5741 (1994); R. Argazzi, C.A. Bignozzi, G.M. Hasselmann, and G.J. Meyer Inorg. Chem. 37, 第18頁、本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公爱） -1 - — - — — --.I- ·-丨-丨丨丨丨訂·丨·丨丨丨丨·線7 (請先閱讀背面之注意事項再填寫本頁) 526488 A7 B7 ·___ 五、發明說明（） (請先閲讀背面之注意事項再填寫本頁) 4533(1998); A.C. Lees, B. Evard, T.E. Keyes, G.J. Vos, C.J. Kleverlaan, M. Alebbi, C.A. Bignozzi Eur. J. Inorg. Chem. 2309 (1999); C.A. Bignozzi, R.A. Argazzi, C.J. Kleverlaan Chem. Soc. Rev· 29, 87 (2000)以上各文獻為本發明共同參考）。金屬錯合物（此後簡稱”（A)”）具有許多種特性，於一較佳實施例中，此種錯合物可吸附於透明的寬能帶.半導體表面上，例如Zr〇2, Ti02，Sn02或ZnO, Nb2〇5或在非晶矽、 Si〇2表面上（此後簡稱”固態基材”），其他適合用於結合或吸附錯合物的基材包含那些能夠於金屬錯合物與固態基材之間形成足夠強連結之基材，此種連結可包含，例如，以酯類和聚氨酸型與聚合物的薄膜鍵結、或矽甲烷型與非晶矽鍵結、或與半導體如鈦、鋅、锆及錫之氧化物鍵結，因此，聚合物的或無機的基材可用於本發明中，亦可製備選錯合物的Luangmuir Blodget(LB)薄膜金（gold)薄層上。 (參見例如共同列為本案參考之 H. Huesmann，C.A. Bignozzi, M.T. Indelli, L. Pavanin, M.A. Rampi, D. Mobius Thin Solid Films. 284, 62 (1996)) 經濟部智慧財產局員工消費合作社印製無論基材是聚合物的、非結晶或微結晶均不影響裝置之效能，此外，基材可為透明的或對於用於偵測光致變色薄膜放射特性變化之光波長不透光；若資料儲存媒介係由 Type I系統所製備可在傳輸模式中被讀取，例如藉由通過一光束至此媒介並偵測傳輸變化，則此基材可被此光波長所穿透；若資料儲存媒介係藉由偵測反射自此媒介之光束變化’則透明的或不透光的固態基材均可使用。第19頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 526488 Α7 Β7 五、發明說明（） (請先閲讀背面之注意事項再填寫本頁) 基材可為一純物質或一混合物，例如錫、鋅及鈥之氧化混合物，及相似的或此類氧化物與非晶硬之混合物，雖然一較佳實施例中基材為一半導體，但基材不需要為半導電的，因此，如上述大多數種類的物質可作為基材，而作為基材的物質係選自不會隱藏吸附的金屬錯合物之能力，用以與配位溶劑或溶液中之配合基進行光取4代反應。金屬錯合物與固態基材之間的連結係由官能基與聚吡啶配合基結合所提供，例如-COOH、-B(OH)2、-P〇3H2 及-R-P〇3Η2，一個此種官能基即足夠結合錯合物至基材表面’金屬錯合物-基材系統之紅外線及拉曼（Raman)光譜顯示羧酸基與鈦或錫氧化物之間連結為部分共價及部分靜電（參見 T.J· Meyer，G.J. Meyer，B.W. Pfennig，J.R. Schoonover，C.J· Timpson，J.F· Wall，C. Kobusch，X· Chen， B.M. Peek, C.G. Wall, W.Ou3 B.W. Erickson, C.A.Bignozzi Inorg. Chem. 33, 3952 (1994); R. Argazzi, C.A. Bignozzi, T.A. Heimer，P.Castellano, G.J. Meyer Inorg. Chem. 33, 5741 (1994))，藉由一個-〇H取代基與基材結合亦可能，所提供的-0H基為一弱酸。經濟部智慧財產局員工消費合作社印製當吸附在固態基材上缺乏溶劑、濕氣及氧氣之下Type ί金屬錯合物顯示顯著的光化學穩定性，當固定在固態基材上此金屬錯合物在配位溶劑（此後簡稱”（Β) ”）或含有配位物種（此後亦簡稱，，（Β)，，）存在下進行有效的光引發反應’以形成新的分子物種（此後簡稱，，（〇，，），此光取代反應較佳發生在（Α)的配合基L上。第20頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）固態基材（A)/(B)之組合適合用於光學資料儲存媒介，（A)選擇的光激發將提升此物種在較高的電子激發態 (此後簡稱”（A*)”），而後續的（A*)將有效地與成份（B)反應以形成一反應產物一新的分子物種（此後簡稱，，（〇，，），並呈現出與（A)不同之吸收光譜。這些製程以方程式（1)及（2)表示： ♦ (A) + hv—(A*) (1) (A*) + (B)-(C) (2) 因此資料可被寫入，藉由將金屬氧化物/(A)系統浸入適當溶劑層下，或者含有特殊配位成份（B)之溶液，並以雷射光束照射（A)以提升（A)至反應態（A*)，（A*)與（B)之反應最後將形成（C)，除去溶劑或配位成份（B)使得反應不可逆，因此資料以數位形式被儲存在固態基材中，以物種（A) 的顏色或放射特性代表數值1，而物種（C)的顏色或放射特性代表數值0，或者反之亦然。資料較佳被讀取為傳送模式’藉由選擇波長在400 nm至800 nm之光譜範圍，其可被成份（A)或成份（C)選擇地吸收，除此之外，當讀取波長之光學密度變化大於一特定值時資料可被讀取為傳送模式。於一較佳實施例中，（B)包含具有強連結場特性的配合基，例如二硫氨基甲酸根、硫氰酸根、氰基、羰基、磷化氫及聚说啶配合基，其中聚，比啶配合基與芳香單元作用顯現長壽命的磷光，具有這些特性的溶劑如氰甲烷亦可使用。於本實施例中，激發的（A*)與（B)反應最後形成一發冷 < 第21頁本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公爱） --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）光成份（C)’若金屬錯合物（A)本質上為發冷光的，成份（B) 將選自那些配合基以產生非發冷光的金屬錯合物（c)，或者產生發光強度不同於（A)的金屬錯合物（c)。利用此種發光物種以讀取儲存資料可能導致一改進的唯謂記憶元件’提供發光分子物種保持一高發光量，較佳高於0.01 ’發光量之偵測係藉由以波長4〇〇至8〇〇 nm 範圍之雷射光束照射結合（A)與（C)之固態基材，且較佳在成份（A)或（C)之最大發光範圍中監測其發光光譜或特定發光波長’然後一元碼可與（A)或（C)發出的冷光存在或不存在產生關聯。若基材使用金屬氧化物，感光分子物種可以沉積在鈦、锆、錫、矽、鈮及鋅之氧化物上與非晶矽一樣，這材料可以膠狀形式產生並沉積在光傳導玻璃或聚合物基材上而得到一薄的透明薄膜，不同厚度的薄膜可利用不同的方法沉積如深度塗佈、絲網印刷法、喷灑塗佈、噴墨印刷或其他習知技術，利用空氣乾燥及接著在溫度範圍約 100-500°C加熱使膠狀的氧化物薄膜黏著在玻璃或聚合物基材上^作為資料儲存裝置的感光薄膜之製造係利用將感光物種（A)吸附在膠狀氧化物薄膜之表面上而完成，其係將半導體薄膜浸入含有感光物種（A)溶解於適當無機或有機溶劑的溶液中而達成，或者，感光物種（A)初步吸附在金屬氧化物粒子之表面上，吸附有物種（A)的粒子再沉積在透明玻璃或聚合物基材上，並在5〇至150°C之間加熱以得到薄的透明薄膜。第22頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公餐) " -- ----· I! I 111 t--— II----I "4^*7 <請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（) 以燈或波長在400-800 nm的雷射光束照射支撐在金屬氧化物上的物種（A)，此光致變色基材之資料儲存能力主要依賴激發及探側雷射的光分解力，考慮覆蓋（A)的金屬氧化物粒子之分佈，其中粒子的平均直徑約在1〇-5〇nm 範圍中，使用直徑相當於那些微粒子直徑的雷射光束將使裝置的光分解達到最大化。 ^ 當資料已利用燈或雷射照射微粒子而光學地寫入，裝置的記錄層則可進一步藉由一層透明聚合物薄膜的薄層保護，此保護層可防止（A)及（C)成份與外界反應物如濕氣及氧氣之間互相反應，於一較佳實施例中，聚合物薄膜包含疏水性的聚合物薄膜，例如聚苯乙晞、聚碳酸、聚乙缔毗啶以及聚甲基甲基丙婦酸酯以防止金屬氧化物與水接觸。 TYPE II系統III II II ^ «— — — — — — I 526488 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Azaphenanthrene is replaced by one or two of the following substituents: -⑶ ^^ , .B (oh) 2, -po3h2 or -RP〇3H 2 (where R is as defined above); 2 2, Yi Hanlin is replaced by one or two of the following substituents: -c〇〇H, β (〇 η) 2, -ΡΟ # 2 or -R-PChH 2 (where R is as defined above), when more than one N_N group is present in the compound (for example, (N-N) 2), these ν_ν groups may be the same or different . Tri-pyridine complexing group in which N-N-N is a chromophore is selected from one, two, or three substituents of the group consisting of: -COOH, Β (〇η) 2, · ρ〇3η2 or -R-PChH2 (where R is as defined above), or substituted by phenyl, wherein phenyl in combination with the following substituents includes: -COOH, -B (OH) 2, -P〇3H2 or -RP〇3H2 (where R is as The above definition), the preferred substituents are in the para position, and when more than one NNN group is present in the compound (eg (NNN) 2), these NNN groups may be the same or different. l Single or multidentate accessory complexes that are not chromophores, such as NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halogen group, NCS_ , N3-, _CH3-, Η ·, oxalate, CO, CN ·, NO, H20, OH., NH3, triazole, pyridine, p-diazabenzene, 4,4'-di-p specific bite, 4, 4'-diisocyanoacetate, 4,4'-di-p-pyridinylacetamidine, 4-cyanopyridine, dibenzonitrile, p-diazepine, N03- or ethyl acetone; or L is A complexing solvent is, for example, acetone, methanol, cyanomethane, acetone, tetrahydrofuran, ethanol, dimethylformamide or dimethyloxythio. Members of such complexes can be prepared according to published methods (e.g., R. Argazzi, CA Bignozzi, TA Heimer, P. Castellano, GJ Meyer Inorg. Chem. 33? 5741 (1994); R. Argazzi, CA Bignozzi, GM Hasselmann, and GJ Meyer Inorg. Chem. 37, p. 18, This paper size applies to China National Standard (CNS) A4 (210 x 297 public love) -1------. I- ·-丨-丨丨丨丨 Ordering · 丨丨丨丨丨 ·· Line 7 (Please read the notes on the back before filling this page) 526488 A7 B7 · ___ V. Description of the invention () (Please read the notes on the back first (Please fill in this page again for matters) 4533 (1998); AC Lees, B. Evard, TE Keyes, GJ Vos, CJ Kleverlaan, M. Alebbi, CA Bignozzi Eur. J. Inorg. Chem. 2309 (1999); CA Bignozzi, RA Argazzi, CJ Kleverlaan Chem. Soc. Rev. 29, 87 (2000) The above references are the common reference of the present invention). Metal complexes (hereinafter referred to as "(A)") have a variety of characteristics. In a preferred embodiment, such complexes can be adsorbed on a transparent wide energy band. Semiconductor surfaces, such as ZrO2, Ti02 , Sn02 or ZnO, Nb205 or on the surface of amorphous silicon and Si02 (hereinafter referred to as "solid substrate"), other suitable substrates for binding or adsorbing complexes include those capable of binding to metal complexes A substrate that forms a sufficiently strong bond with a solid substrate, such a bond may include, for example, a thin film bond to the polymer with an ester and a polyamic acid type, or a silicon methane type to an amorphous silicon bond, or Bonded with semiconductors such as titanium, zinc, zirconium, and tin oxides. Therefore, polymer or inorganic substrates can be used in the present invention, and Luangmuir Blodget (LB) thin film gold (gold) ) On a thin layer. (See, for example, H. Huesmann, CA Bignozzi, MT Indelli, L. Pavanin, MA Rampi, D. Mobius Thin Solid Films. 284, 62 (1996), which are commonly listed as references in this case.) No matter the substrate is polymer, amorphous or microcrystalline, it does not affect the performance of the device. In addition, the substrate may be transparent or opaque to the wavelength of light used to detect changes in the radiation characteristics of the photochromic film. The storage medium is prepared by the Type I system and can be read in the transmission mode. For example, by passing a light beam to the medium and detecting the transmission change, the substrate can be penetrated by the wavelength of the light. If the data storage medium is borrowed, By detecting the change of the light beam reflected from this medium, transparent or opaque solid substrates can be used. Page 19 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 526488 Α7 Β7 V. Description of the invention () (Please read the precautions on the back before filling this page) The substrate can be pure Substance or a mixture, such as an oxidized mixture of tin, zinc, and ', and the like or a mixture of such oxides with amorphous hardness. Although a substrate is a semiconductor in a preferred embodiment, the substrate need not be semi-conductive. It is conductive, so most kinds of substances as above can be used as the base material, and the material as the base material is selected from the ability not to hide the adsorbed metal complex, and used to coordinate with the complexing solvent or the complex in the solution. Perform light generation 4 generation reaction. The connection between the metal complex and the solid substrate is provided by the combination of a functional group and a polypyridine complex, such as -COOH, -B (OH) 2, -P〇3H2, and -RP〇3Η2, one such function Infrared and Raman spectra of the metal complex-substrate system are sufficient to bind the complex to the surface of the substrate. The bond between the carboxylic acid group and titanium or tin oxide is partially covalent and partially electrostatic ( See TJ · Meyer, GJ Meyer, BW Pfennig, JR Schoonover, CJ · Timpson, JF · Wall, C. Kobusch, X · Chen, BM Peek, CG Wall, W. Ou3 BW Erickson, CABignozzi Inorg. Chem. 33, 3952 (1994); R. Argazzi, CA Bignozzi, TA Heimer, P. Castellano, GJ Meyer Inorg. Chem. 33, 5741 (1994)), it is also possible to bind to the substrate with a -OH substituent, provided The -0H group is a weak acid. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs When adsorbed on a solid substrate lacks solvents, moisture and oxygen. Type ί metal complex shows significant photochemical stability. When immobilized on a solid substrate, the metal complex The compound performs an effective photo-initiated reaction in the presence of a coordination solvent (hereinafter referred to as "(Β)") or contains a coordinated species (hereinafter also referred to as, (B) ,,) to form a new molecular species (hereinafter referred to as "hereinafter (,, (〇 ,,)) This photo-substitution reaction preferably occurs on the complex group L of (Α). Page 20 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 526488 Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative A7 B7 V. Description of the invention () The combination of solid substrate (A) / (B) is suitable for optical data storage media. (A) The selected light excitation will enhance this species at higher levels Electronic excited state (hereinafter referred to as "(A *)"), and subsequent (A *) will effectively react with component (B) to form a reaction product and a new molecular species (hereinafter referred to as ,, (0 ,,, ), And shows that (A) does not The absorption spectra of these processes are expressed by equations (1) and (2): ♦ (A) + hv— (A *) (1) (A *) + (B)-(C) (2) Write, by immersing the metal oxide / (A) system under an appropriate solvent layer, or a solution containing a special coordination component (B), and irradiating (A) with a laser beam to raise (A) to a reactive state ( The reaction between A *), (A *) and (B) will eventually form (C), removing the solvent or coordination component (B) makes the reaction irreversible, so the data is stored digitally in a solid substrate and the species ( The color or emission characteristic of A) represents a value of 1, and the color or emission characteristic of species (C) represents a value of 0, or vice versa. The data is preferably read as a transmission mode by selecting a wavelength between 400 nm and 800 nm The spectral range can be selectively absorbed by the component (A) or the component (C). In addition, when the optical density of the reading wavelength changes more than a specific value, the data can be read as the transmission mode. In a preferred embodiment, (B) contains a complexing group having strong linking field characteristics, such as dithiocarbamate, thiocyanate, cyano, and carbonyl Phosphine and polypyridine complexes, in which poly-pyridine complexes interact with aromatic units to exhibit long-life phosphorescence. Solvents with these characteristics such as methyl cyanide can also be used. In this example, the excited (A *) The reaction with (B) results in a chill < page 21 This paper size applies the Chinese National Standard &CN; CNS) A4 specification (210 X 297 public love) ------------- ------- Order --------- line (please read the precautions on the back before filling this page) 526488 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description () Light component (C) 'If the metal complex (A) is luminescent in nature, the component (B) will be selected from those metal complexes (c) that are complexed to produce non-luminous light, or produce a different luminous intensity The metal complex (c) in (A). The use of such light-emitting species to read stored data may result in an improved so-called memory element that provides a light-emitting molecular species that maintains a high light emission, preferably higher than 0.01 '. The detection of the light emission is performed at a wavelength of 400 to A laser beam in the 800 nm range irradiates a solid substrate combining (A) and (C), and preferably monitors its emission spectrum or specific emission wavelength in the maximum emission range of component (A) or (C) 'then The unary code can be associated with the presence or absence of the cold light emitted by (A) or (C). If a metal oxide is used for the substrate, the photosensitive molecular species can be deposited on the oxides of titanium, zirconium, tin, silicon, niobium, and zinc. Like amorphous silicon, this material can be produced in colloidal form and deposited on light-transmitting glass or polymer. To obtain a thin transparent film on a substrate, and different thickness films can be deposited by different methods such as deep coating, screen printing, spray coating, inkjet printing or other conventional techniques, using air drying and Then, it is heated at a temperature range of about 100-500 ° C to make the colloidal oxide film adhere to the glass or polymer substrate. The manufacture of the photosensitive film as a data storage device uses the adsorption of the photosensitive species (A) on the colloidal oxide. It is completed by immersing a semiconductor film in a solution containing a photosensitive species (A) dissolved in a suitable inorganic or organic solvent, or the photosensitive species (A) are initially adsorbed on the surface of the metal oxide particles. The particles adsorbed with the species (A) are then deposited on a transparent glass or polymer substrate and heated between 50 and 150 ° C. to obtain a thin transparent film. Page 22 This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 meals) "----- · I! I 111 t --- II ---- I " 4 ^ * 7 < Please read the notes on the back before filling out this page) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Supported by a lamp or laser beam with a wavelength of 400-800 nm Species (A) on metal oxides. The data storage capacity of this photochromic substrate mainly depends on the photodecomposition force of the excitation and probe lasers. Consider the distribution of metal oxide particles covering (A), where the average of the particles With a diameter in the range of about 10-50 nm, the use of a laser beam with a diameter equivalent to the diameter of those particles will maximize the device's photodecomposition. ^ When the data has been written optically by irradiating the particles with a lamp or laser, the recording layer of the device can be further protected by a thin layer of a transparent polymer film. This protective layer can prevent (A) and (C) components and External reactants such as moisture and oxygen react with each other. In a preferred embodiment, the polymer film includes a hydrophobic polymer film, such as polyphenylene terephthalate, polycarbonate, polyethyleneimide, and polymethyl Methylpropionate to prevent metal oxides from coming into contact with water. TYPE II system

Type II系統包含光感應的光異構化分子，光異構化反應為不可逆的’光異構化分子吸收與原始分子不同波長的光，其光吸收的差異可用為儲存資料的方法。於一實施例中，Type II系統包含一透明的聚合物薄膜或非晶矽支撐及具有兩種電子激發態特性的過度金屬錯合物’其中之一為光反應的傾向於一異構化反應。金屬錯合物可被吸附在非晶矽表面或分散在聚合物薄膜中，異構化反應包含分子成份的内部鍵結或内部電子結構改變，並導致發光分子永久的顏色改變，此分子内部電子結構的光感應變型可發生在流體溶液中，或當分子吸附在非第23頁本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公餐y --------------------^---------^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 526488 A7 B7 五、發明說明（）晶矽上或包含於透明聚合物薄膜中時。於一實施例中，用於Type II系統的金屬錯合物包含正菠二烯配合基，其藉由一氰基橋接至一個或兩個四胺基釕中的部分，該部分可透過異菸鹼酸配合基的酸酸官能基連接金屬氧化物支撐的表面，或透過吡啶單位的氮連接 py-COOH配合基而配位在釕中心，或透過p比咬單.位的氮連接py-P〇3H2或py-CH2-P〇3H2官能基而配位在釣中心，當金屬錯合物被包含在透明的聚合物基板中時，適當的配合基包含py-C〇OH、py-P〇3H2及py-CH2-P〇3H2的酉旨類，酉旨類的碳氫基較佳含有1至6個碳原子，最好是1至3個碳原子。於一較佳實施例中，使用甲基或乙基醋，例如py-COOCH3 、 py-P03HCH3 、 py-CH2-P03HCH3 、 py-COOCH2CH3、py-P03HCH2CH3 及 py-CH2-P03HCH2CH3，當比較錯合物對碳酸基或磷酸基時，這些酯類官能基增進錯合物在聚合物（如聚乙埽吡啶以及聚甲基甲基丙埽酸酯）中之溶解度。 TYPE II系統之較佳實施例中，此型的單核與多核過度金屬錯合物一樣以下列分子式表示： [trans-HOOCpyRun(NH3)4-NC-nor-CN]2+ {[trans-HOOCpyRun(NH3)4-NC]2-nor}4+ [trans-CH3-OOCpyRun(NH3)4-NC-nor-CN]2+ {[trans-CH3-OOCpyRun(NH3)4-NC]2-nor}4+ [trans_CH3CH2-OOCpyRuu(NH3)4-NC-nor-CN]2+ {[trans-CH3CH2-〇OCpyRuII(NH3)4-NC]2-nor}4+ 第24頁本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） ---------------丨丨訂·丨1!鍊 (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7_ 五、發明說明（）其中HOOCpy為異菸鹼酸；CH3-OOCpy為異菸鹼酸的甲基酯， CH3CH2-〇〇Cpy為異於驗酸的乙基酯，trans為以銜（Ru)為中心之結構，以及NC-nor-CN為二氰正菠二烯配合基。當以 UV 範圍的光照射時這些錯合物進行顏色變化，但若以波長大於5OOnm光照射則起始顏色不受影響。這些物種之吸收光譜在可見光範圍具有強烈的吸收帶，此種吸收係因為 MLCT由Ru(II)中心的d軌道轉變至位於HOOCpy及NC-nor-CN配合基的反鍵結7C*(antibonding*)軌道，以及藉由在 UV範圍中強烈的LC吸收帶，由於位於HOOCpy及NC-nor-CN配合基的π-π*轉變。當這些類型分子物種以UV照射時，發生正菠二婦異構化為四環烯，並伴隨正菠二烯部分軌道的電子轉變強度損失，此造成在UV及可見光範圍的吸收光譜消除，當錯合物以波長大於500nm光照射時，起始吸收光譜被觀察到無變化。本發明之TYPE II系統係利用一電荷轉移錯合物包含一配位正菠二婦配合基，此錯合物顯示光致變色反應只有當位於正茨二晞配合基的L C態（例如π - π *態）被佔用，光致變色反應通常藉由照射UV光激發金屬錯合物而得到。本發明之另一較佳實施例中，TYPE II裝置亦可考慮使用下列分子式之過度金屬錯合物： [trans-HOOCpyRun(X4)-NC-nor-CN]2+ {[trans-HOOCpyRun(X4)-NC]2-nor}4+ [trans-CH3-OOCpyRun(X4)-NC-nor-CN]2+ {[trans-CH3-OOCpyRun(X4)-NC]2-nor}4+ 第25頁本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) --- ----丨訂---------' 經濟部智慧財產局員Η消費合作社印製 526488 A7 B7 五、發明說明（） [trans-CH3CH2-OOCpyRun(X4)4-NC-nor-CN]2+ {[trans-CH3CH2-OOCpyRun(X4)4-NC]2-nor}4+ 其中 X4代表聚氮雜（polyaza)或聚硫代（polythio)大環例如 N4(CH2)l0或S4(CH2)10，下列分子式之物種也可考慮： [M(N_N)2(NC-nor-CN)(L)]n [M(N-N)2(NC-nor-CN)2]n , [M(N-N)2(X)(NC-nor-CN)M(N-N)2(L)]n [M(N-N-N)(NC-nor-CN)(L)2]n [M(N-N-N)2(NC-nor-CN)2(L)]n [M(N-N-N)2(L)2(NC-nor-CN)M(N-N-N)2(L)2]n 其中總電荷術數n非特別指定，而係由金屬中心氧化態數及配合基電荷數之代數總和所產生，一般當下述過度金屬錯合物被使用時，η值將由-1 2變化至+6，以不同的過度金屬錯合物或可變化至此範圍外。Μ為過渡金屬，較佳地為鈷、鐵或鍊，但更佳地為鐵或釕。Ν-Ν為發色團聚说啶配合基，例如；未取代的2,2’-二毗啶基或被下列一個或兩個取代基取代-COOH、-COOC2H5、-cooch3、-β(οη)2、 -Ρ03Η2或-R-P03H 2(其中 R為一飽和或一芳香碳氫官能基，例如亞甲基、乙基、丙基等，或是苯基）；未取代.的 1，1〇-二氮雜菲或被下列一個或兩個取代基取代-COOH、-COOC2H5、-cooch3、-b(oh)2、-Ρ03Η2 或-R-P03H2(其中 R如上述定義）；未取代的2,2’-二喳啉或被下列一個或兩個取代基取代- COOH、-COOC2H5、-cooch3、-b(oh)2、 -Ρ03Η2或-R-P03H 2(其中R如上述定義）；N-N-N為未取代第26頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線· 526488 經濟部智慧財產局員工消費合作社印製 A7 B7__ 五、發明說明（）的發色團三p比淀配合基或被下列一個、兩個或三個取代基取代-COOH、-COOC2H5、-COOCH3、-B(0H)2、-Ρ03Η2 或 -R-P03H 2(其中R如上述定義），或是被苯基取代，其中苯基為未取代或被下列取代基取代<0011、-<：00<：2115、-cooch3、-b(oh)2、-po3h2 或-R-P03H 2(其中 R 如上述定義），較佳地這些苯基取代基細係在對位（？&[&)上*。若超過一個N-N或N-N-N出現在錯合物中，則個別的N-N或 N-N-N可相同或不同。L為非發色團的單齒或多齒附屬配合基，例如鹵素基、NCS·、草酸基、CO、CN·、NO、毗啶、 H20、ΟΙΓ、NH3、二乙烯二乙氨、N02-、NC-(CH2)2-CN、 NC-(CH2)3-CN、NC-(CH2)4-CN、ΝΓ、-CH3、Η·、三岐、對二氮雜苯、4,4、二吡啶、4,4，-二吡啶基乙烷、4,4、二吡啶基乙晞、4-氰毗啶、二氰苯、二乙婦二乙氨、Ν02·、乙醯丙酮，或強的配位溶劑如氰甲坡、水、乙醯丙S同、二甲基氧硫基或二甲基甲醯胺，若超過一個L配合基出現在錯合物中，則個別的配合基L可相同或不同。值得注意的是[M(N-N)2(X)(NC-nor-CN)M(N-N)2(L)]n 及 [M(N-N-N)2(L)2(NC-nor-CN)M(N-N-N)2(L)2]n 為雙核物種，其中二氰正茨二婦作為金屬中心之間的橋接配合基。又一實施例中，二氰二氰正菠二缔配合基（NC-nor-CN) 可被一個具有兩個吡啶單元透過碳原子在對位共價連結的正菠二埽取代，或透過一或二個亞甲基間隔（例如 py- nor-py; py-CH2-nor-CH2-py; py-(CH2)2-nor-(CH2)2-py) 0 [M(N-N)2(NC-nor-CN)(L)]n、[M(N-N)2(NC-nor-CN)2]n、[M(N- 第27頁本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐i -----丨丨丨丨丨丨i-丨丨丨丨丨訂·丨丨丨丨丨丨線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 526488 A7 B7 _ 五、發明說明（） N)2(X)(NC-nor-CN)M(N-N)2(L)]n、[M(N-N-N)(NC-nor-CN)(L)2]n、 [M(N-N-N)2(NC-nor-CN)2(L)]n 及[M(N-N-N)2(L)2(NC-nor-CN)M(N-N-N)2(L)2]n之一重要特徵為MLCT態之出現，其包含聚毗啶配合基之π *軌道，一旦軌道填滿，這些狀態立即退回基態及關於MLCT態含有正菠二晞配合基之π*軌道之較低能階。 * TYPE III 系統 TYPE III系統包含一光致變色材料，其係沉積一適當的組合過度金屬錯合物（作為分子感光劑）及一寬能帶半導體透明薄膜上之電子接收劑，此半導體例如三氧化鎢、氧化鈦、二氧化鋅、或二氧化錫，較佳地為微結晶的二氧化鈦。TYPE III系統之運作係藉由一固態半導體基材具有一空的導電帶能夠作為吸收分子感光劑所釋放的電子之輸送管道，此分子感光劑（此後簡稱”（S)”）吸收可見光，此程序提升（S)至電子激發態可發射電子至半導體導電帶，電子發射為快速的且與激發態（S)之放射與非放射衰退競爭，且將與激發態化學反應競爭。吸附在半導體表面的第二組成份（此後簡稱”（Q)”）接收來自半導體的電子而得到穩定的還原態（Q1。TYPE III裝置之功能見第15圖之說明’於第 15圖中，一分子感光劑（S)發射一電子進入二氧化鈦基材之導電帶，於此步驟中進行顏色變化（此為一退色的吸收光譜）由黃色（未氧化態）至白色（氧化態），電子接收劑接收此電子，於此步驟中進行顏色變化由藍色（未還原態）至紅色（還原態）。傳統上更戲劇性的光變化為觀察電子接收劑第28頁本紙張尺度適用尹國國家標準（CNS)A4規格（210 X 297公釐） ϋ n n ϋ It a·^ in «ϋ n · *_1 n n n n n n 一OJ· n flu n ϋ n ϋ n t t I f (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）的還原反應更甚分子感光劑的氧化反應，傳統上，分子感光劑與電子接收劑雨者之顏色變化的淨結果可被測量，然而，若分子感光劑或電子接收劑其中之一有較強烈的顏色變化，而另一者之顏色變化較少察覺，則較強顏色變化者可被測量。此種支撐於透明玻璃或聚合物基材的材料之光致變化特徵係與包容於雨者之間的電子轉移步驟有關，其可系統化為下列方程式（3)及（4): (S)/Ti02/(Q) + hv - (S + )/Ti027(Q) (3) (S + )/Ti02./(Q) 一（S + )/Ti02/(Q·) (4) 特別地，顏色變化係由於形成感光劑氧化態（S + )及電子接收劑還原態（Ql，（S + )與（Q)之間電荷重組，如下列方程式（5)所示，緩慢地恢復材料原始的顏色： S + /Ti02/Q- — S/Ti02/Q (5) 此原始顏色亦可藉由電荷分離系統S + /Ti02/Q_與氧分子反應而緩慢地恢復。揭示的光致變色材料係用於當其暴露且持續地照射可見光時維持電荷分離形式s+/Ti〇2/(T的顏色，當材料的照光中斷時恢復成S/Ti02/Q形式的原始顏色，因此，TYPE III系統只有在預期其將持續地暴露在適當波長的光之下時才適用於長期穩定資料儲存。有用的分子感光劑（S)可選自已知的以聚说啶配合基為基礎的過度金屬錯合物（參見，C.A.Bignozzi，J.R. Schoonover， F· Scandola Progr· Inorg· Chem· 44，1-95 (1997); R. Argazzi，C.A. 第29頁本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） ------------MW-------- *訂---------祿·— (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7_ 五、發明說明（）The Type II system contains light-induced photoisomerization molecules. The photoisomerization reaction is irreversible. The photoisomerization molecule absorbs light at different wavelengths from the original molecule. The difference in light absorption can be used as a method for storing data. In one embodiment, the Type II system includes a transparent polymer film or amorphous silicon support and a transition metal complex with two electronic excited state characteristics. One of the two is a photoreaction-prone isomerization reaction. . Metal complexes can be adsorbed on the surface of amorphous silicon or dispersed in polymer films. The isomerization reaction involves the internal bonding of molecular components or changes in the internal electronic structure, and causes the permanent color of the light-emitting molecule to change. The light-sensitive variant of the structure can occur in a fluid solution, or when molecules are adsorbed on a non-page 23 page. This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 public meals) ---------- ---------- ^ --------- ^ (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Consumption Cooperative 526488 A7 B7 V. Invention Explanation () When it is on crystalline silicon or contained in a transparent polymer film. In one embodiment, the metal complex used in the Type II system includes an orthodienyl complex, which is bridged to one or A part of two tetraamine ruthenium, which can be coordinated to ruthenium through the acid-acid functional group of the isonicotinic acid complex to the metal oxide-supported surface, or through the pyridine unit nitrogen to the py-COOH complex. Py-P〇3H2 or py-CH2-P at the center or through a single bit of nitrogen. The 3H2 functional group is coordinated at the fishing center. When the metal complex is contained in a transparent polymer substrate, suitable complexing groups include py-COOOH, py-P〇3H2, and py-CH2-P〇3H2. The hydrocarbyl group of the molybdenum group preferably contains 1 to 6 carbon atoms, and most preferably 1 to 3 carbon atoms. In a preferred embodiment, methyl or ethyl vinegar is used, such as py -COOCH3, py-P03HCH3, py-CH2-P03HCH3, py-COOCH2CH3, py-P03HCH2CH3, and py-CH2-P03HCH2CH3. When comparing the complex to carbonate or phosphate, these ester functional groups enhance the complex in Solubility in polymers (such as polyacetamidine and polymethylmethylpropionate). In a preferred embodiment of the TYPE II system, this type of mononuclear and multinuclear transition metal complex is represented by the following formula : [Trans-HOOCpyRun (NH3) 4-NC-nor-CN] 2+ {[trans-HOOCpyRun (NH3) 4-NC] 2-nor} 4+ [trans-CH3-OOCpyRun (NH3) 4-NC-nor -CN] 2+ {[trans-CH3-OOCpyRun (NH3) 4-NC] 2-nor} 4+ [trans_CH3CH2-OOCpyRuu (NH3) 4-NC-nor-CN] 2+ {[trans-CH3CH2-〇OCpyRuII (NH3) 4-NC] 2-nor} 4+ Page 24 This paper applies Chinese national standards (CNS) A4 specification (210 χ 297 mm) --------------- 丨 Order · 1! Chain (Please read the precautions on the back before filling this page) 526488 Economy Printed by the Consumers ’Cooperative of the Ministry of Intellectual Property Bureau A7 B7_ 5. Description of the invention () where HOOCpy is isonicotinic acid; CH3-OOCpy is a methyl ester of isonicotinic acid, and CH3CH2-〇〇Cpy is an ethyl ester different from acid test Ester, trans is a structure centered on Ru (Ru), and NC-nor-CN is a dicyano-n-spinadiene complex. These complexes undergo a color change when irradiated with light in the UV range, but the initial color is not affected if irradiated with light with a wavelength greater than 500 nm. The absorption spectrum of these species has a strong absorption band in the visible range. This absorption is due to the MLCT transition from the d orbital of the Ru (II) center to the anti-bonding 7C * (antibonding *) located in the HOOCpy and NC-nor-CN complex ) Orbits, and with a strong LC absorption band in the UV range, due to the π-π * transitions of the HOOCpy and NC-nor-CN ligands. When these types of molecular species are irradiated with UV, isomerization of orthodyne to tetracycline occurs, and the electron transition intensity loss of some orbitals of orthodadiene occurs, which results in the elimination of the absorption spectrum in the UV and visible light ranges. When the complex is irradiated with light with a wavelength greater than 500 nm, no change in the initial absorption spectrum is observed. The TYPE II system of the present invention utilizes a charge transfer complex containing a coordinated orthostilbene complex. This complex shows a photochromic reaction only when it is in the LC state (eg, π- π * state) is occupied, and the photochromic reaction is usually obtained by irradiating UV light to excite the metal complex. In another preferred embodiment of the present invention, the TYPE II device may also consider using a transition metal complex of the following molecular formula: [trans-HOOCpyRun (X4) -NC-nor-CN] 2+ {[trans-HOOCpyRun (X4 ) -NC] 2-nor} 4+ [trans-CH3-OOCpyRun (X4) -NC-nor-CN] 2+ {[trans-CH3-OOCpyRun (X4) -NC] 2-nor} 4+ Page 25 This paper size applies to China National Standard (CNS) A4 specification (210 x 297 mm) (Please read the precautions on the back before filling this page) ----------- Order --------- '' Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative 526488 A7 B7 V. Description of the invention () [trans-CH3CH2-OOCpyRun (X4) 4-NC-nor-CN] 2+ {[trans-CH3CH2-OOCpyRun (X4) 4 -NC] 2-nor} 4+ where X4 represents a polyaza or polythio ring such as N4 (CH2) 10 or S4 (CH2) 10. Species with the following formulas are also considered: [M (N_N) 2 (NC-nor-CN) (L)] n [M (NN) 2 (NC-nor-CN) 2] n, [M (NN) 2 (X) (NC-nor-CN) M (NN) 2 (L)] n [M (NNN) (NC-nor-CN) (L) 2] n [M (NNN) 2 (NC-nor-CN) 2 (L)] n [M (NNN ) 2 (L) 2 (NC-nor-CN) M (NNN) 2 (L) 2] n where the total charge number n is not specifically specified, but is determined by the number of metal center oxidation states and the charge of the ligand The algebraic sum generated, typically when the following transition metal complexes are used, the value of [eta] changes by -12 to +6, with different fault or transition metal compound may be far outside the range of variation. M is a transition metal, preferably cobalt, iron or a chain, but more preferably iron or ruthenium. Ν-Ν is a chromophore group, such as a pyridine complex, for example; unsubstituted 2,2'-dipyridyl or substituted with one or two of the following substituents -COOH, -COOC2H5, -cooch3, -β (οη) 2, -P03Η2 or -R-P03H 2 (where R is a saturated or an aromatic hydrocarbon functional group, such as methylene, ethyl, propyl, etc., or phenyl); unsubstituted 1,1. -Diazaphenanthrene or substituted by one or two of the following substituents -COOH, -COOC2H5, -cooch3, -b (oh) 2, -P03Η2 or -R-P03H2 (where R is as defined above); unsubstituted 2 , 2'-dioxoline or substituted by one or two of the following substituents-COOH, -COOC2H5, -cooch3, -b (oh) 2, -P03Η2 or -R-P03H 2 (where R is as defined above); NNN In order not to replace page 26, this paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- line · 526488 Printed by A7 B7__ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. The chromophore three p ratio complex of the invention description () or substituted by one, two or three of the following -COOH, -COOC2H5, -COOCH3 , -B ( 0H) 2, -P03Η2 or -R-P03H 2 (where R is as defined above), or is substituted by phenyl, wherein phenyl is unsubstituted or substituted by the following substituents < 0011,-<: 00 <: 2115, -cooch3, -b (oh) 2, -po3h2 or -R-P03H 2 (where R is as defined above), preferably these phenyl substituents are in the para position (? &Amp; [&) *. If more than one N-N or N-N-N is present in the complex, the individual N-N or N-N-N may be the same or different. L is a non-chromophore monodentate or multidentate auxiliary complex, such as halogen, NCS ·, oxalate, CO, CN ·, NO, pyridine, H20, ΟΓ, NH3, diethylenediethylamine, N02- , NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, ΝΓ, -CH3, Η ·, Sanki, p-diazabenzene, 4, 4, 2 Pyridine, 4,4, -dipyridylethane, 4,4, dipyridylacetamidine, 4-cyanopyridine, dicyanobenzene, diethyldiamine, N02, acetamidine, or strong Coordination solvents such as cyanomethoxane, water, acetonitrile, dimethyloxythio, or dimethylformamide. If more than one L complex is present in the complex, the individual complexes L may be Same or different. It is worth noting that [M (NN) 2 (X) (NC-nor-CN) M (NN) 2 (L)] n and [M (NNN) 2 (L) 2 (NC-nor-CN) M ( NNN) 2 (L) 2] n is a binuclear species, in which dicyano diazine is used as a bridging ligand between metal centers. In yet another embodiment, the cyanocyanuric ortho-dithronine complex (NC-nor-CN) may be replaced by an ortho-dithizone having two pyridine units covalently linked at the para position through a carbon atom, or through a Or two methylene intervals (e.g. py- nor-py; py-CH2-nor-CH2-py; py- (CH2) 2-nor- (CH2) 2-py) 0 [M (NN) 2 (NC -nor-CN) (L)] n, [M (NN) 2 (NC-nor-CN) 2] n, [M (N- page 27) This paper size applies Chinese National Standard (CNS) A4 specifications (210 χ 297 mmi ----- 丨丨丨丨丨丨 i- 丨丨丨丨 Ordering 丨丨丨丨丨丨丨 Line (Please read the notes on the back before filling this page) Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the employee consumer cooperative 526488 A7 B7 _ V. Description of the invention () N) 2 (X) (NC-nor-CN) M (NN) 2 (L)] n, [M (NNN) (NC-nor-CN ) (L) 2] n, [M (NNN) 2 (NC-nor-CN) 2 (L)] n and [M (NNN) 2 (L) 2 (NC-nor-CN) M (NNN) 2 An important feature of (L) 2] n is the emergence of the MLCT state, which contains the π * orbitals of the polypyridine complex. Once the orbit is filled, these states immediately return to the ground state. Lower energy level of π * orbit. * TYPE III system TYPE III system package Contains a photochromic material, which is deposited with a suitable combination of excessive metal complex (as a molecular photosensitizer) and an electron receiving agent on a wide band semiconductor transparent film, such as tungsten trioxide, titanium oxide, Zinc oxide, or tin dioxide, preferably microcrystalline titanium dioxide. The operation of the TYPE III system is to use a solid semiconductor substrate with an empty conductive tape that can serve as a transport channel for absorbing electrons released by molecular photosensitizers. The molecular photosensitizer (hereinafter referred to as "(S)") absorbs visible light. This procedure promotes (S) to the electronically excited state to emit electrons to the semiconductor conduction band. The electron emission is fast and the radiation and non-radiation of the excited state (S) Decline competition and will compete with the excited state chemical reaction. The second component (hereinafter referred to as "(Q)") adsorbed on the semiconductor surface receives electrons from the semiconductor to obtain a stable reduced state (for the function of the Type III device, see Explanation of FIG. 15 'In FIG. 15, a molecule of the photosensitizer (S) emits an electron into the conductive tape of the titanium dioxide substrate. In this step, The color change (this is a faded absorption spectrum) changes from yellow (unoxidized state) to white (oxidized state). The electron acceptor receives this electron. In this step, the color change is changed from blue (unreduced state) to red ( (Reduced state). Traditionally, the more dramatic light change is to observe the electron-receiving agent. Page 28 This paper applies the National Standard (CNS) A4 specification (210 X 297 mm). Ϋ nn ϋ It a · ^ in «ϋ n · * _1 nnnnnn I OJ · n flu n ϋ n ϋ ntt I f (Please read the precautions on the back before filling this page) 526488 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Reduction of Invention Description () The reaction is more than the oxidation reaction of molecular photosensitizers. Traditionally, the net result of the color change of molecular photosensitizers and electron receivers can be measured. However, if one of the molecular photosensitizers or electron receivers has a stronger color Change, while the other one's color change is less noticeable, the stronger color change can be measured. The photo-induced change characteristics of the material supported on the transparent glass or polymer substrate are related to the electron transfer steps contained in the rain, which can be systematized into the following equations (3) and (4): (S) / Ti02 / (Q) + hv-(S +) / Ti027 (Q) (3) (S +) / Ti02 ./ (Q)-(S +) / Ti02 / (Q ·) (4) In particular, The color change is due to the formation of a charge recombination between the oxidized state (S +) of the photosensitizer and the reduced state (Ql, (S +) and (Q) of the electron acceptor). As shown in the following equation (5), the original material is slowly restored. Color: S + / Ti02 / Q- — S / Ti02 / Q (5) This original color can also be recovered slowly by the charge separation system S + / Ti02 / Q_ reacting with oxygen molecules. Revealed photochromic material It is used to maintain the color of the charge separation form s + / Ti〇2 / (T when it is exposed and continuously irradiated with visible light. When the light of the material is interrupted, it is restored to the original color of S / Ti02 / Q. Therefore, the TYPE III system It is suitable for long-term stable data storage only when it is expected to be continuously exposed to light of an appropriate wavelength. Useful molecular sensitizers (S) may be selected from the known polyisopropyl ligands Based on transition metal complexes (see, CABignozzi, JR Schoonover, F. Scandola Progr. Inorg. Chem. 44, 1-95 (1997); R. Argazzi, CA. Page 29 This paper applies Chinese national standards (CNS) A4 specification (21〇x 297 mm) ------------ MW -------- * Order --------- Lu · — (Please (Please read the notes on the back before filling out this page) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of Invention ()

Bignozzi, T.A. Heimer, G.J. Meyer Inorg. Chem. 36, 2(1997); J.A. Moss，R. Argazzi, C.A. Bignozzi，G.J. Meyer Inorg. Chem. 36, 762(1997); R. Argazzi, C.A. Bignozzi, T.A. Heimer, F.N. Castellano, G.J. Meyer J. Phys. Chem. 1015 2591 (1997); R. Argazzi, C.A. Bignozzi，G. Hasselmann，and G.J· Meyer Inorg. Chem. 37, 4533(1998); C.G. Garcia, N.Y. Marakami Iha? R. Argazzi, C.A. Bignozzi J. Photochem. Photobiol. A: Chemistry 115, 239(1998); M.T. Indelli, C.A. Bignozzi, F. Scandola, J.P. Collin Inorg. Chem. 37, 6084(1998); C.A. Bignozzi, R.A. Argazzi, C.J. Kleverlaan Chem. Soc. Rev. 29, 87 (2000))，這些金屬錯合物以下列分子式表示： [M(N-N)2L2]n [M(N-N)L4]n [M(N-N-N)L3]n [M(N-N-N)2]n 其中n為錯合物總電荷數，非特別指定，為金屬中心氧化態數及配合基電荷的代數總和，Μ為一過渡金屬包含銘、錄、銅、銀、飽、舶、鍊、鐵或姥，但最佳為鐵或釘。 Ν-Ν為發色團的聚吡啶配合基，例如2,2’-二毗啶結合下列群組之一或二個取代基包含：-COOH、-Β(ΟΗ)2、-Ρ〇3Η2 或-R-P03H 2(其中R為一飽和或一芳香碳氫官能基，例如亞甲基、乙基、丙基等，或是苯基）；1，10-二氮雜菲由下列一或二個取代基所取代：-COOH、-B(OH)2、-Ρ03Η2或 -R-P〇3H 2(其中R如上述定義）；2,2’-二喹啉由下列一或二個取代基所取代：-COOH、-B(OH)2、-P〇3H2 或-R-P03H 2(其第30頁本紙張尺度適用中國國家標準(CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線. 526488 A7 B7 五、發明說明（） <請先閱讀背面之注意事項再填寫本頁) 中R如上述定義），當超過一個N-N基出現在化合物中時 (例如（N-N)2)，這些N-N基部份可相同或不同。n-N-N為發色團的三毗啶配合基結合選自下列群組之一、二或三個取代基包含：-COOH、-B(0H)2、-Ρ03Η2 或-R-P03H2(其中 R 如上述定義）’或被苯基所取代，其中苯基結合下列取代基包含：-COOH、-B(OH)2、-P〇3H2 或-R-P〇3H2(其中 r 如上述定義）’較佳的取代基在對位（para position)，當超過一個N-N-N基出現在化合物中時（例如（n-N-N)2)，這些N-N-N基可相同或不同。L為發色團的聚毗淀配合基，可相同或不同，其為未取代或由下列取代基所取代：-COOH、 -B(0H)2、-PO3H2或-R-P〇3H2(其中R如上述定義），或是非發色團的單齒或多齒附屬配合基，例如NC-(CH2)2-CN、 NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、NCS.、N3-、-CH3·、 Η、草酸基、CO、CN-、NO、Η20、0Η·、NH3、對二氮雜苯、4,4，-二吡啶、4,4’-二吡啶基乙烷、4,4，-二毗啶基乙晞、 ***、吡啶、4-氰毗啶、二苯甲腈、二乙晞二乙氨、乙醯丙酮或NO/。或者，新構思的分子感光劑亦可使用，此範例包含經濟部智慧財產局員工消費合作社印製 [(4,4’-HP03CH2)2bpyRu(CN)4]4-、[(4,4，-HP03)2bpyRu(CN)4]4、 (4,4、HP03CH2)2bpyRe(C0)3(X)、[(dcbH2)2Ru(CN)4]4,及（4,4，-HP03)2(bpy)Re(C0)3(X),其 X 為 CN-、NCS.、py、NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、CO、NO、吡啶、4-氰吡啶、二苯甲晴、H2〇、NH3或NO2-。適用的電子接收劑可選自過度金屬錯合物結構I及第31頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 526488 A7 B7 五、發明說明（ II : Η"Α-ιτ 1-4Bignozzi, TA Heimer, GJ Meyer Inorg. Chem. 36, 2 (1997); JA Moss, R. Argazzi, CA Bignozzi, GJ Meyer Inorg. Chem. 36, 762 (1997); R. Argazzi, CA Bignozzi, TA Heimer , FN Castellano, GJ Meyer J. Phys. Chem. 1015 2591 (1997); R. Argazzi, CA Bignozzi, G. Hasselmann, and GJ Meyer Inorg. Chem. 37, 4533 (1998); CG Garcia, NY Marakami Iha R. Argazzi, CA Bignozzi J. Photochem. Photobiol. A: Chemistry 115, 239 (1998); MT Indelli, CA Bignozzi, F. Scandola, JP Collin Inorg. Chem. 37, 6084 (1998); CA Bignozzi, RA Argazzi, CJ Kleverlaan Chem. Soc. Rev. 29, 87 (2000)), these metal complexes are represented by the following molecular formula: [M (NN) 2L2] n [M (NN) L4] n [M (NNN) L3 ] n [M (NNN) 2] n where n is the total charge number of the complex, not specifically specified, is the algebraic sum of the number of metal center oxidation states and the charge of the complex, and M is a transition metal containing inscriptions, records, copper, Silver, full, ship, chain, iron, or iron, but the best is iron or nail. N-N is a polypyridine complex of a chromophore, for example, 2,2'-dipyridine in combination with one or two of the following groups contains: -COOH, -B (ΟΗ) 2, -PO3Η2 or -R-P03H 2 (where R is a saturated or aromatic hydrocarbon functional group, such as methylene, ethyl, propyl, etc., or phenyl); 1,10-diazaphenanthrene consists of one or two of the following With 2 substituents: -COOH, -B (OH) 2, -P03Η2 or -RP〇3H 2 (where R is as defined above); 2,2'-diquinoline is replaced by one or two of the following substituents : -COOH, -B (OH) 2, -P〇3H2 or -R-P03H 2 (the page size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm)) (Please read the back first (Notes on this page, please fill in this page) Order --------- line. 526488 A7 B7 V. Description of the invention () < Please read the notes on the back before filling in this page) R as defined above), When more than one NN group is present in the compound (eg (NN) 2), these NN group portions may be the same or different. nNN is a chromophore of a tripyridyl complex, and one or two or three substituents selected from the group consisting of -COOH, -B (0H) 2, -P03Η2, or -R-P03H2 (where R is as described above) Definition) 'or substituted by phenyl, wherein phenyl in combination with the following substituents comprises: -COOH, -B (OH) 2, -P03H2 or -RP〇3H2 (where r is as defined above)' The bases are in the para position. When more than one NNN base is present in the compound (eg (nNN) 2), these NNN bases may be the same or different. L is a polypyridine complex of a chromophore, which may be the same or different, and is unsubstituted or substituted with the following substituents: -COOH, -B (0H) 2, -PO3H2, or -RP〇3H2 (where R is as (As defined above), or non-chromophore monodentate or multidentate accessory complexes, such as NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halogen groups, NCS., N3-, -CH3 ·, hydrazone, oxalate, CO, CN-, NO, Η20, 0Η ·, NH3, p-diazabenzene, 4,4, -dipyridine, 4,4'-dipyridine Ethane, 4,4, -dipyridinylacetamidine, triazole, pyridine, 4-cyanopimidine, dibenzonitrile, diethylammonium diethylamine, acetamidine, or NO /. Alternatively, a newly-conceived molecular photosensitizer can also be used. This example includes printing by [[4,4'-HP03CH2) 2bpyRu (CN) 4] 4-, [(4,4,- HP03) 2bpyRu (CN) 4] 4, (4,4, HP03CH2) 2bpyRe (C0) 3 (X), [(dcbH2) 2Ru (CN) 4] 4, and (4,4, -HP03) 2 (bpy ) Re (C0) 3 (X), where X is CN-, NCS., Py, NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halo , CO, NO, pyridine, 4-cyanopyridine, benzophenone, H2O, NH3 or NO2-. The applicable electron-receiving agent can be selected from the transition metal complex structure I and page 31. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 526488 A7 B7 V. Description of the invention (II: Η " Α-ιτ 1-4

1-5 I L7 Λβ r11 •12 7T2~Lla -101-5 I L7 Λβ r11 • 12 7T2 ~ Lla -10

LuLu

II (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製其中L至L6表示配合基連接至金屬中心。 L表一配合基，其進一步藉一共價鍵修改為a，A表示適用於與基材相互作用之部分，例如吨淀類配合基被_ C00H、-b(oh)2、-P〇3H2 或-R-P03H2 於對位取代，其中 R 為碳氫間隔基，於一較佳實施例中，此間隔基為共輛的或是芳香性的，共軛的或是芳香性的間隔基出現增加錯合物之莫耳衰退常數（molar extinction coefficient, ε )，結果增加顏色強度。其他間隔基如分支或直鍊飽和碳氫化合物、分支或直鍊非共軛未飽和碳氩化合物'或者碳環基亦可適用為間隔基，此間隔基可包含延著骨幹額外的碳氫取代基，較佳的間隔基骨幹包含一最小碳原子數，如此使電子轉移距離最短，因而增加電子轉移，於一較佳實施例中’ 間隔基可使用最高具有七個碳原子的骨幹，雖然更長骨幹亦適用。 Β表示橋接配合基提供兩金屬部分Mi及Μ2之間穩定第32頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） a I μ·· I t km ^ 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）的連結，適用的橋接配合基包含二齒的（bidentate)配合基及任何其他能夠橋接兩金屬部分的配合基，一些適用的橋接配合基包含Cl' CN·、4,4，-二吡啶、NCS、對二氮雜苯、 n2、〇及otr，但並不限定。 L至L6與L7至L14 一樣為單齒或多齒配合基，可選自 NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、li 素基、NCS.、草酸基、CO、CN-、NO、毗啶、4-氰吡啶、二苯甲腈、H2〇、〇Η·、NH3、二乙烯二乙氨、n〇2_、未取代或甲基取代的 2,2、二毗啶及未取代或甲基取代的ι，10-二氮雜菲。Ml及 M2為過度金屬離子選自週期表中過度金屬第一、第二及第三族，其能夠進行氧化態的可逆變化，適用的金屬中心包含銅、鈷、鎳、銥、鈀、鍊、餓或鍺，最隹地為鐵或釕。於另一較佳實施例中，多核金屬錯合物結構上相似於 Π，但更多核數亦可使用（多於兩個金屬中心彼此連接）。 TYPE III光致變色裝置之製備可利用將包含半導體之薄膜’如二氧化鈦支撐於玻璃或聚合材料上，浸入含有分子感光劑（S)及電子接收劑（Q)之溶液中，具有此兩物種之表面覆蓋物與其在溶液中之分子濃度成比例，1:丨莫耳比之（S)與（Q) ’則相同量之兩物種被吸附在半導體粒子上；或者，（S)與（Q)可吸附在半導體的懸浮粒子表面，然後沉積在固態基板如玻璃或聚合材料上^ 例如，一種使用TYPE III系統製造光學資料儲存媒介之方法包含： (i) 挺供一種分子感光劑，以下列任一分子式表第331 本紙張尺度適用中國國家標準（CNS)A4規格(210 X 297公釐了 (請先閱讀背面之注意事項再填寫本頁) 訂---------線· 526488 A7 B7 經濟部智慧財產局員工消費合作社印製五、發明說明（不 · [M(N-N)2L2]n [M(N-N)L4]n [M(N-N-N)L3]n 及 [M(N-N-N)2]n . 其中Μ為具有一種氧化態之過度金屬； Ν-Ν為發色團的聚吡啶配合基，具有一個電荷且可結合下列群組之一至二個取代基包含·· -COOH、-Β(〇η)2、-P03H2、-R-P03H2及苯基，其中R為一飽和或一芳香碳氮官能基； N-N-N為發色團的三v比淀配合基，具有一個電荷且可結合選自下列群組之一至三個取代基包含：_(：〇〇11、-β(ΟΗ)2、-P03H2、-R-P〇3H2及苯基，其中苯基可結合選自下列群組之一個或多個取代基包含：_c〇〇H、-B(〇h)2、· P〇3H2或-R-P〇3H2，其中R為一飽和或一芳香碳氫官能基； L為具有-電荷之非發色團單齒或多齒附屬配合基；及 ri為總電荷數，包含金屬中心氧化態數及配合基電荷的代數總和； (ii)彳疋供一種電子接收劑，以下列任一分子式表示：第34頁 (請先閱讀背面之注意事項再填寫本頁) -n ϋ n n ·ϋ ·ϋ ϋ 一aI*· i ϋ 1 I ϋ an an an I . 526488 A7 B7 五、發明說明（ L，一 A — L〆 L' 及 l/L. L A—Μ·-Β-—.jyi*- 經濟部智慧財產局員工消費合作社印製其中A為说淀被選自下列群組之一部分取代基於對位取代包含-COOH、-B(0H)2、-P〇3H2 或-R-PO3H2 ’ 其中 R為一飽和或一芳香碳氫官能基；， B為橋接配合基， L，，其可相同或不同，為選自下列群組之一配合基包含：NC-(CH2)2-CN、NC-(CH2)3-CN、nc-(ch2)4-cn、鹵素基、 NCS-、草酸基、CO、CN·、NO、毗啶、4-氰毗啶、二苯甲腈、Η20、ΟΗΓ、NH3、二乙婦二乙氨、NO,、未取代或甲基取代的2,2’-二吡啶、以及未取代或甲基取代的M0-二氮雜菲；及 M’，其可相同或不同，為能夠進行氧化態的可逆變化之過度金屬； (iii) 提出一基材包含一寬能帶半導體；及 (iv) 吸附分子該感光劑與該電子接收劑之精確混合物於該基材上，因而形成一分子感光-電子接收-基材系統。此基材可以是非晶形、單晶及選自下列群組之三氧化鎢、二氧化鈦、二氧化鋅、或二氧化錫，此基材可包含膠體形式的粒子，其中粒子具有一平均直徑範圍由約1 〇 nm 至約50 nm. 此實施例之步驟（iii)可包含沉積膠體形式之半導體於第35頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公楚） ί請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）一支撐物上，此支撐物包含光穿透玻璃或透明聚合物材料，以及之後在溫度約10(TC至約500t之間加熱該沉積的半導體。步驟（iv)包含將基材浸入分子感光劑與電子接收劑之溶液中，將基材移出溶液及乾燥基材。步驟（iv)可選擇地包含以分子感光劑與電子择收劑之溶液混合膠體狀半導體，乾燥該膠體狀半導體，沉積該膠體狀半導體於一支撐物上，此支撐物包含光穿透玻璃或透明聚合物材料，以及之後在溫度約50°C至約150°C之間加熱該沉積的半導體可增加一額外的步驟（v)，其包含以光照射該系統之一區域，藉以使分子感光劑吸收此光並射出一電子進入基材 2的導電帶，其中氧化態分子感光劑與還原態電子接收劑之間產生電荷分離，其中氧化態分子感光劑具有一不同於未氧化狀態分子感光劑的吸收光譜，且還原態電子接收劑具有一不同於未還原狀態電子接收劑的吸收光譜。亦可利用另一額外的步驟（vi)，其包含將一透明聚合物薄膜之薄塗層塗在記錄層之表面上。於一較佳實施例中，噴墨技術用於沉積已吸附（S)與 (Q)之膠體狀半導體粒子於一基材上，在喷墨列印時，，墨，，係由列印頭之噴嘴噴出像透過一媒介，不同於噴墨技術包含，例如，熱噴墨，其中墨被加熱以產生氣泡直到壓力迫使其爆發並碰撞該媒介；以及恩電嘴墨，其中當施以電流時在墨儲存槽背面之壓力結晶收縮，因而將墨滴推出嘴第36頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----------J----------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 526488 A7 _____ B7 五、發明說明（）嘴。於一較佳實施例中，用於喷墨印表機的，，墨，，包含已吸附（S)與（Q)之膠體狀半導體粒子於適當液體中的懸浮液，例如水，選擇地具有其他組成份（其他染料、溶劑、添加物及相似物），藉由適當的媒介”墨”可被列印包含任何表面其可吸附或黏附半導體粒子，適用的表面包含但不限定紙、塑膠、玻璃及相似物。利用其他列印技術塗濃適當液體中或粉末形式的半導體粒子於不同的媒介亦可考慮，例如絲網印刷、雷射列印、平版印刷、微影及其它相似技術等。範例較佳實施例現以三種型式光致變色材料之一系列的實驗範例說明，此些範例僅用於說明非用以限定本發明之範圍。分析儀器錯合物之1H NMR光譜於300 MHz及25。(：中被記錄在 Varian Gemini 300光譜儀中，使用Bruker 200光譜儀在 25 °C及81 MHz中或利用Varian Gemini 300光譜儀於121 MHz及25°C中偵測npyHiNMR光譜，化學位移在百萬分之一至高頻的 85% H3P〇4中，UV可見光光譜被記錄在 Lambda 40 Perkin Elmer 光譜儀中〇馇用『RiUdcH^bkakl錯合物為Type I裝f 第37頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)II (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where L to L6 indicate that the base is connected to the metal center. L is a complexing group, which is further modified to a by a covalent bond, and A represents a part suitable for interaction with the substrate. For example, a ton-type complex is _ C00H, -b (oh) 2, -P〇3H2 or -R-P03H2 is substituted in the para position, where R is a hydrocarbon spacer. In a preferred embodiment, the spacer is co- or aromatic, and the conjugate or aromatic spacer is increased. The molar extinction coefficient (ε) of the complex results in an increase in color intensity. Other spacers such as branched or straight-chain saturated hydrocarbons, branched or straight-chain non-conjugated unsaturated argon hydrocarbons, or carbocyclic groups may also be suitable as spacers. This spacer may contain additional hydrocarbon substitutions along the backbone. The preferred spacer base backbone contains a minimum number of carbon atoms, which minimizes the electron transfer distance and therefore increases electron transfer. In a preferred embodiment, the spacer can use backbones with up to seven carbon atoms, although more Long backbones are also applicable. Β indicates that the bridging complex provides stability between the two metal parts Mi and M2. Page 32 The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) a I μ ·· I t km ^ 526488 Ministry of Economic Affairs wisdom Printed by A7 B7, Consumer Cooperatives of the Property Bureau. 5. The connection of invention description (). Suitable bridging complexes include bidentate complexes and any other complexes that can bridge two metal parts. Some suitable bridging complexes. Cl 'CN ·, 4,4, -dipyridine, NCS, p-diazabenzene, n2, 0, and otr are included, but are not limited. L to L6 is the same as L7 to L14. It is a monodentate or multidentate complex. It can be selected from NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, li. , NCS., Oxalate, CO, CN-, NO, pyridine, 4-cyanopyridine, dibenzonitrile, H2O, 〇 ··, NH3, diethylenediethylamine, no2_, unsubstituted or 2,2-Dipyridine and unsubstituted or methyl substituted ι, 10-diazaphenanthrene. Ml and M2 are transition metal ions selected from the transition metal groups 1, 2, and 3 of the periodic table. They can undergo reversible changes in the oxidation state. Suitable metal centers include copper, cobalt, nickel, iridium, palladium, chains, Hunger or germanium, most iron or ruthenium. In another preferred embodiment, the multi-core metal complex is similar in structure to Π, but more core numbers can be used (more than two metal centers are connected to each other). TYPE III photochromic devices can be prepared by supporting thin films containing semiconductors such as titanium dioxide on glass or polymeric materials and immersing them in solutions containing molecular photosensitizers (S) and electron-accepting agents (Q). The surface covering is proportional to its molecular concentration in the solution. 1: Moore's ratio (S) and (Q) 'are the same amount of the two species adsorbed on the semiconductor particles; or, (S) and (Q) Can be adsorbed on the surface of suspended particles of semiconductors and deposited on solid substrates such as glass or polymeric materials ^ For example, a method for manufacturing optical data storage media using the TYPE III system includes: (i) a molecular photosensitizer, using any of the following A molecular formula table No. 331 This paper size is applicable to China National Standard (CNS) A4 specifications (210 X 297 mm (please read the precautions on the back before filling this page). Order --------- line · 526488 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (No · [M (NN) 2L2] n [M (NN) L4] n [M (NNN) L3] n and [M (NNN) 2 ] n. where M is a transition metal having an oxidation state; Ν- A polypyridine complex that is a chromophore and has one charge and can bind to one or two of the following groups: -COOH, -B (〇η) 2, -P03H2, -R-P03H2 and phenyl, Where R is a saturated or an aromatic carbon-nitrogen functional group; NNN is a tri-v ratio complex of a chromophore, which has a charge and can be combined with one to three substituents selected from the group consisting of: _ (: 〇〇 11, -β (ΟΗ) 2, -P03H2, -RP〇3H2 and phenyl, wherein phenyl can be combined with one or more substituents selected from the group consisting of: -c〇〇H, -B (〇h) 2. · P〇3H2 or -RP〇3H2, where R is a saturated or an aromatic hydrocarbon functional group; L is a non-chromophore monodentate or multidentate auxiliary complex with-charge; and ri is the total charge number , Including the algebraic sum of the oxidation number of the metal center and the charge of the complex; (ii) 彳疋 For an electron receiving agent, expressed by any of the following molecular formulas: Page 34 (Please read the precautions on the back before filling this page)- n ϋ nn · ϋ · ϋ ϋ-aI * · i ϋ 1 I ϋ an an an I. 526488 A7 B7 V. Description of the invention (L, 1 A — L〆L 'and 1 / L. LA-M -Β -—. Jyi *-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where A is said to be partially replaced by one selected from the group consisting of para-based substitutions including -COOH, -B (0H) 2, -P. 3H2 or -R-PO3H2 'where R is a saturated or an aromatic hydrocarbon functional group;, B is a bridging complex, L, which may be the same or different, and is selected from one of the following groups. The complex includes: NC- (CH2) 2-CN, NC- (CH2) 3-CN, nc- (ch2) 4-cn, halo, NCS-, oxalate, CO, CN, NO, pyridine, 4-cyanopyridine, Dibenzonitrile, Η20, ΟΗΓ, NH3, diethyldiethylamine, NO ,, unsubstituted or methyl substituted 2,2'-dipyridine, and unsubstituted or methyl substituted MO-diazaphenanthrene ; And M ', which may be the same or different, are transition metals that can undergo a reversible change in oxidation state; (iii) propose a substrate containing a wide band semiconductor; and (iv) adsorb molecules to the photosensitizer and the electron receiver The precise mixture of agents is on the substrate, thus forming a molecular photo-electron receiving-substrate system. The substrate may be amorphous, single crystal, and tungsten trioxide, titanium dioxide, zinc dioxide, or tin dioxide selected from the group consisting of colloidal particles, wherein the particles have an average diameter ranging from about 10 nm to about 50 nm. Step (iii) of this embodiment may include depositing a semiconductor in the form of colloids on page 35. This paper is scaled to the Chinese National Standard (CNS) A4 (210 X 297). Please read first. Note on the back, please fill in this page again) 526488 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention () A support that contains light penetrating glass or transparent polymer material, and The deposited semiconductor is heated at a temperature of about 10 ° C. to about 500 t. Step (iv) includes immersing the substrate in a solution of a molecular photosensitizer and an electron receiving agent, removing the substrate from the solution, and drying the substrate. Step (iv) Optionally, the colloidal semiconductor is mixed with a solution of a molecular photosensitizer and an electron selective agent, the colloidal semiconductor is dried, and the colloidal semiconductor is deposited on a support. The object comprises light penetrating glass or a transparent polymer material, and subsequent heating of the deposited semiconductor at a temperature of about 50 ° C to about 150 ° C may add an additional step (v), which includes irradiating the system with light A region through which the molecular photosensitizer absorbs this light and emits an electron into the conductive band of the substrate 2, wherein a charge separation occurs between the oxidized molecular photoreceptor and the reduced electron receiver, and the oxidized molecular photoreceptor has a different The absorption spectrum of the molecular photosensitizer in the unoxidized state, and the reduced electron acceptor has an absorption spectrum different from that of the unreduced electron acceptor. Another additional step (vi) may also be used, which includes converting a transparent polymer A thin coating of the film is applied to the surface of the recording layer. In a preferred embodiment, inkjet technology is used to deposit colloidal semiconductor particles that have adsorbed (S) and (Q) onto a substrate, and then inkjet During printing, the ink is ejected from the nozzle of the print head through a medium, unlike inkjet technology, which includes, for example, thermal inkjet, where the ink is heated to generate air bubbles until the pressure forces Eruption and collision with the medium; and Endian nozzle ink, in which the pressure crystallizes on the back of the ink storage tank when the current is applied, so the ink drops are pushed out of the nozzle. Page 36 This paper applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) ---------- J ---------- Order --------- Line (Please read the precautions on the back before filling this page ) 526488 A7 _____ B7 V. Description of the invention () Mouth. In a preferred embodiment, the inks used in inkjet printers include colloidal semiconductor particles that have adsorbed (S) and (Q) on Suspensions in suitable liquids, such as water, optionally have other components (other dyes, solvents, additives, and the like), and can be printed with the appropriate medium "ink" including any surface that can adsorb or adhere to semiconductors Particles, suitable surfaces include, but are not limited to, paper, plastic, glass, and the like. Other printing techniques can be used to thicken semiconductor particles in appropriate liquid or powder forms in different media, such as screen printing, laser printing, lithography, lithography, and other similar technologies. Examples The preferred embodiment is illustrated by a series of experimental examples of one of three types of photochromic materials. These examples are only used to illustrate and not limit the scope of the present invention. Analytical instrument The 1H NMR spectrum of the complex is at 300 MHz and 25. (: Was recorded in a Varian Gemini 300 spectrometer, using a Bruker 200 spectrometer at 25 ° C and 81 MHz or using a Varian Gemini 300 spectrometer to detect npyHiNMR spectra at 121 MHz and 25 ° C, with chemical shifts in parts per million In the high frequency 85% H3P〇4, the UV visible light spectrum is recorded in the Lambda 40 Perkin Elmer spectrometer. The use of "RiUdcH ^ bkakl complex is Type I. f. Page 37 This paper applies Chinese national standards ( CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page)

訂---------線I 經濟部智慧財產局員工消費合作社印製經濟部智慧財產局員工消費合作社印製 526488 A7 _____B7__ 五、發明說明（）以微結晶的二氧化锆及二氧化鈦為基礎的透明薄膜依據文獻中所記載之方法製備並沉積於玻璃上（R. Argazzi， C.A. Bignozzi, T.A. Heimer, P. Castellano, G.J. Meyer. Inog. Chem. 33，5741 (1994); T.A. Heimer，S.T· D’Arcangelis，F. Farzad，J.M· Stipkala and G.J. Meyer Inog· Chem· 35, 5319 (1996))，然後此薄膜透過吸附下列金屬錯合物於微結晶寬能帶半導體表面上而功能化：Order --------- Line I Printed by the Consumers 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by 526488 A7 _____B7__ V. Description of the Invention () Microcrystalline zirconia and titanium dioxide Based transparent films were prepared according to the methods described in the literature and deposited on glass (R. Argazzi, CA Bignozzi, TA Heimer, P. Castellano, GJ Meyer. Inog. Chem. 33, 5741 (1994); TA Heimer, ST · D'Arcangelis, F. Farzad, JM · Stipkala and GJ Meyer Inog · Chem · 35, 5319 (1996)), and then the film was functionalized by adsorbing the following metal complexes on the surface of a microcrystalline wide band semiconductor :

Ru(dcH2b)2(COO)2Ru (dcH2b) 2 (COO) 2

Ru(dcH2b)2(Cl)2Ru (dcH2b) 2 (Cl) 2

Ru(dcH2b)2(NCS)2 [Fe(trpy)(C00H)3]2(C104)2 其中 dcKhb 為 2,2’-二吡淀- 4,4’-二叛酸，而（typy)(COOH)3 為4,4’，4”-三幾基-2,2’：6’，2”-三说症，這些物種係依據文獻中所記載之方法製備（M.K. Nazeeruddin，A· Kar，I· Rodlcio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzal. J. Am. Chem· Soc. 1 15, 6382 (1993); R. Argazzi，C.A· Bignozzi，T.A. Heimer，P. Castellano, G.J. Meyer. Inog· Chem· 33, 5741 (1994))。薄膜透過將該透明薄膜沉浸於1 (T4 M甲醇或乙醇的染料溶液中而得到具有光學密度高於〇·6(—般約在1-2範圍中），此薄膜在60°C下乾燥，然後浸沒於氰甲烷薄層下並以150W Xe燈或Nd-YAG雷射在可見光範圍中照射，照光後之顏色變化觀察如第1圖至第4圖所示。第1圖至第4圖顯示金屬氧化物透明薄膜照光之前與之後的吸收光譜，其分別結合下列染料分子·· 第38頁本紙張尺度適用中國國家標準（CNS)A4規格⑽x 297公爱） ' ----------- ------丨丨訂i丨丨丨_丨丨-線Η (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 526488 A7 ____B7 _ 五、發明說明（）Ru (dcH2b) 2 (NCS) 2 [Fe (trpy) (C00H) 3] 2 (C104) 2 where dcKhb is 2,2'-dipyridine-4,4'-diacidic acid, and (typy) ( COOH) 3 is 4,4 ', 4 "-triquinyl-2,2': 6 ', 2" -trisomy, and these species are prepared according to the methods described in the literature (MK Nazeeruddin, A. Kar, I. Rodlcio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzal. J. Am. Chem. Soc. 1 15, 6382 (1993); R. Argazzi, CA Bignozzi, TA Heimer, P. Castellano, GJ Meyer. Inog. Chem. 33, 5741 (1994)). The film was immersed in 1 (T4 M methanol or ethanol dye solution to obtain an optical density higher than 0.6 (typically in the range of 1-2). The film was dried at 60 ° C. Then immersed in a thin layer of cyanomethane and irradiated in the visible light range with a 150W Xe lamp or Nd-YAG laser, and the color change observation after illumination is shown in Figures 1 to 4. Figures 1 to 4 show The absorption spectrum of the metal oxide transparent film before and after light irradiation, which combines the following dye molecules, respectively. Page 38 This paper applies the Chinese National Standard (CNS) A4 specification (x 297). -------- --- ------ 丨丨 Order i 丨丨丨 _ 丨丨 -Line Η (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 526488 A7 ____B7 _ 5 , Description of the invention ()

Ru(dcH2b)2(CO〇)2 Ru(dcH2b)2(Cl)2 Ru(dcH2b)2(NCS)2 [Fe(trpy)(C00H)3]2(C104)2 第5圖說明彩色的變化與二氧化锆薄膜及吸附的 Ru(dcH2b)2(L)2染料在氰甲烷存在下光反應之關聯（l係選自下列群組NCS·、C1·及二乙基二硫代氨基甲酸酯）。第6 圖說明彩色的變化與二氧化锆薄膜及吸附的 [Fe(trpy)(C00H)3]2(C104)2染料在氰甲烷存在下光反應之關聯。彩色的變化係由於包含錯合物d-*(dcH2b)MLCT激發.?！與说甲说洛劑之取代反應’金屬聚π比咬錯合物之激發態反應性傾向於同質溶液中光取代反應，如先前所述（詳見 T.J. meyer， Pure and app 1 ied Chemistry 5 8， 1 1 93 (1993))，值得注意的是此份研究並未延伸至金屬錯合物吸附異相的半導體材料或非晶矽，亦無文獻揭示使用此種金屬錯合物於資料儲存媒介中。資料係藉由短於600nm波長的光照射該裝置而光學地儲存’該波長較佳地在400-5OOnm範圍中，可利用波長大於550nm光束而讀取該資料❹以此方式儲存資料，該裝置必須被保護以避免與周遭的濕氣互相反應，其可能造成染料緩的去吸附或包含水分子的光取代反應，保護可藉由塗佈一層透明聚合物薄膜於光學裝置上，該薄膜在乾的氬蒸氣下去除其表面之水份，在全力未過濾的15〇w Xe 燈照射下，Ru(dcH2b)2(COO)2、Ru(dcH2b)2(Cl)2 及第39頁本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公餐） _ . (請先閱讀背面之注意事項再填寫本頁)Ru (dcH2b) 2 (CO〇) 2 Ru (dcH2b) 2 (Cl) 2 Ru (dcH2b) 2 (NCS) 2 [Fe (trpy) (C00H) 3] 2 (C104) 2 Figure 5 illustrates the change in color Correlation with photoreaction of zirconium dioxide film and adsorbed Ru (dcH2b) 2 (L) 2 dye in the presence of cyanomethane (I is selected from the group NCS ·, C1 · and diethyldithiocarbamic acid ester). Figure 6 illustrates the relationship between the change in color and the photoreaction of the zirconium dioxide film and the adsorbed [Fe (trpy) (C00H) 3] 2 (C104) 2 dye in the presence of methyl cyanide. The color change is caused by the inclusion of the complex d-* (dcH2b) MLCT.?! With the substitution reaction of the said agent, the metal polyπ ratio of the bite complex is excited toward the photoreaction in a homogeneous solution, as described previously (see TJ meyer, Pure and app 1 ied Chemistry 5 8 , 1 1 93 (1993)), it is worth noting that this study did not extend to the adsorption of heterogeneous semiconductor materials or amorphous silicon by metal complexes, and there is no literature revealing the use of such metal complexes in data storage media. . The data is stored optically by illuminating the device with light shorter than 600 nm in wavelength. The wavelength is preferably in the range of 400-5OO nm, and the data can be read using a light beam with a wavelength greater than 550 nm. The device stores the data in this way. Must be protected to avoid interaction with the surrounding moisture, which may cause slow desorption of the dye or photo-replacement reactions containing water molecules. Protection can be achieved by coating a transparent polymer film on the optical device. Remove the water on the surface under the argon vapor. Ru (dcH2b) 2 (COO) 2, Ru (dcH2b) 2 (Cl) 2 and the paper size on page 39 under the irradiation of a fully unfiltered 15w Xe lamp. Applicable to China National Standard (CNS) A4 specification (210 X 297 meals) _. (Please read the precautions on the back before filling this page)

526488 A7 B7 五、發明說明（）526488 A7 B7 V. Description of the invention ()

Ru(dcH2b)2(NCS)2金屬錯合物在透明二氧化錯上之光化學穩定性顯示於第7圖至第9圖中，在該些實驗中，裝置係維持在乾的氬蒸氣中’第7圖至第9圖亦描述觀察比較光學裝置在氰甲烷存在下光譜相對於時間之變化。第10圖描述觀察Zr〇2薄膜吸附Ru(dcH2b)2(NCS)2 錯合物在配位的2,2’-二说咬配合基（bpy)濃度約q 1M存在下照光之光譜變化。光譜變化為NCS·配合基與取代的二吡啶之光譜變化一致，由取代NCS·配合基，可觀察到其放射光譜改變，初始的放射光譜中心在75Onm且特徵為 Ru(dcH2b)2(NCS)2錯合物在Zr02薄膜上，被不同的放射光譜所取代，其中心在 660nm 且特徵為 [Ru(dcH2b)2(bpy)2]2 +錯合物吸附在Zr02薄膜上。使用『Ru(dcHg_b)g_(NCCHjJ)^l2 +錯合物為 Type I 裝置依據公開的方法製備[Ru(dcH2b)2(Cl)2]錯合物（M.K. Nazeeruddin, A. Kar, I. Rodlcio，R. Humphry-Baker，Ε· Muller, P. Liska, N. Vlachopoulos, M. Gratzal. J. Am. Chem. Soc. 1 1 5, 6382 (1 993))，[Ru(dcH2b)2(NCCH3)2]2 +錯合物則藉由溶解[Ru(dcH2b)2(Cl)2]於甲醇與超過兩倍莫耳 .數的三氟甲烷磺酸銀或六氟磷酸銀中，此溶液被熱迴流三個小時，然後在旋轉式蒸發器中乾燥，再加入氰甲烷.，過濾該溶液，然後在熱迴流額外的8小時，再濃縮該溶液並且加入***使氰甲烷錯合物沉澱，此錯合物以矽膠做管柱第40貫本紙張尺度適用中國國家標準（CNS)A4規格（210x 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線i 經濟部智慧財產局員工消費合作社印製 526488 A7 B7 五、發明說明（）層析及元素分析而純化，亦可得到錯合物之NMR光譜， lH NMR：59.52 d 1Ηχ2? J 6Hz; 9.12 s 2H; 8.96 s 2H; 8.35 dd 2H，J2 Hz; 7.8 d 2H，J 6Hz; 7·7 dd 2H，J 6Hz，J 2Hz 0 复驗結果以微結晶二氧化錘與二氧化鈦為基礎的透的薄膜被製備及如上述沉積於玻璃上，該些薄膜透過吸附 [Ru(dcH2b)2(NCCH3)2]2+錯合物而功能化，其中兩個氰甲烷分子透過氮端及氰基橋接Ru(II)離子，吸附作用係藉由在溫度約25-40°C將二氧化锆或二氧化鈦薄膜於錯合物的 1 (Τ4Μ氰甲烷溶液中沉浸8小時，另一吸附方法為係在無光狀態下由氰甲烷錯合物的甲醇或丙酮溶液中形成。第 11a 圖顯示[Ru(dcH2b)2(NCCH3)2]2 +錯合物（光譜 Α) 在Zr02薄膜上並浸於含有0.1M四丁基氣化銨（TBAC1)中觀察所得之光譜變化。以未過濾1 50W Xe燈照射該薄膜造成由初始光譜（A)至最後光譜（B)之快速變化，該些光譜變化與配位的氰甲烷以氯進行光取代之結果一致，以大於 55Onm波長之光照射該乾燥薄膜觀察並無進一步之光譜變化。光取代反應發生之時間刻度係由雷射快閃光解實驗所決定，[Ru(dcH2b)2(NCCH3)2]2+錯合物的甲醇溶液在 0·1Μ TBAC1存在下利用紅寶石雷射與Nd-YAG雷射之激發光束照射，光束以2-5mJ加上5-7ns半寬之脈衝傳送。第1 lb圖顯示[Ru(dcH2b)2(NCCH3)2]2 +錯合物之雷射激發第41頁本紐尺度適用中關家標準(CNS)A4規格（21G X 297公釐)' " 一 (請先閱讀背面之注意事項再填寫本頁> 訂---------線i 經濟部智慧財產局員Η消費合作社印製 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）接著在吸收峰中心5 50nm出現後由於以氯取代CH3CN(圖形標示B的部分），製程在時間刻度5〇ns時完成。類似的反應亦發生在四丁基氨NCS (TBANCS)存在下的錯合物，吸附[以11((1(：11213)2^(：(：113)2]2 +錯合物之21：02薄膜在0.1M TBANCS與甲醇中以150W Xe燈照射，光譜變化與形成[Ru(dcH2b)2(NCS)2]2 +之結果一致，值得注意的是’氰甲烷錯合物轉變成含NCS-衍生物由於配位NCS基的彈性模式，亦伴隨放射波峰中心在75Onm的出現及出現強紅外線吸收帶在2 1 0 0 c m -1。使用「Ru(4,4，-bpyCH1P〇iH1)1(NCCHy1l2+錯合物為 Type I 裝置製備 rRuH^-bpvCt^PC^HyyNCCHygl2. 配合基製備 4，4’-二乙氧羰基-2,2’-二毗啶（1)The photochemical stability of Ru (dcH2b) 2 (NCS) 2 metal complex on transparent dioxide is shown in Figures 7 to 9. In these experiments, the device was maintained in dry argon vapor 'Figures 7 to 9 also describe the observation of the change in the optical spectrum of the comparative optical device over time in the presence of methyl cyanide. Fig. 10 depicts the observation of the light spectrum of the Ru (dcH2b) 2 (NCS) 2 complex adsorbed on the ZrO2 film in the presence of a coordinated 2,2'-bisorbine complex (bpy) concentration of about q 1M. The spectral change is the same as that of the substituted dipyridine of the NCS · complex. The substitution of the NCS · complex shows the change in the emission spectrum. The initial emission spectrum center is 75nm and is characterized by Ru (dcH2b) 2 (NCS). The 2 complex is replaced on the Zr02 film by different emission spectra, its center is at 660 nm and it is characterized by [Ru (dcH2b) 2 (bpy) 2] 2+ complex adsorbed on the Zr02 film. [Ru (dcHg_b) g_ (NCCHjJ) ^ l2 ++ complex is a Type I device and a [Ru (dcH2b) 2 (Cl) 2] complex (MK Nazeeruddin, A. Kar, I. Rodlcio) , R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzal. J. Am. Chem. Soc. 1 1 5, 6382 (1 993)), [Ru (dcH2b) 2 (NCCH3 ) 2] 2+ complex is dissolved in methanol and more than twice the molar number of silver trifluoromethanesulfonate or silver hexafluorophosphate by dissolving [Ru (dcH2b) 2 (Cl) 2]. This solution is Heat reflux for three hours, then dry in a rotary evaporator, then add cyanomethane. Filter the solution, then heat reflux for an additional 8 hours, concentrate the solution and add ether to precipitate the cyanomethane complex. The complex is made of silica gel for column 40th. The paper size is applicable to Chinese National Standard (CNS) A4 (210x 297 mm) (Please read the precautions on the back before filling this page). Order ------- --Line i Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 526488 A7 B7 V. Description of the invention () Purification by chromatography and elemental analysis, NMR spectrum of the complex can also be obtained, lH NMR: 59.52 d 1Η χ2? J 6Hz; 9.12 s 2H; 8.96 s 2H; 8.35 dd 2H, J2 Hz; 7.8 d 2H, J 6Hz; 7 · 7 dd 2H, J 6Hz, J 2Hz Based on thin films were prepared and deposited on glass as described above, these films were functionalized by adsorbing [Ru (dcH2b) 2 (NCCH3) 2] 2+ complex, in which two cyanomethane molecules penetrated the nitrogen end And cyano-bridged Ru (II) ions, the adsorption effect is by immersing a zirconium dioxide or titanium dioxide film in a complex 1 (T4M cyanomethane solution for 8 hours at a temperature of about 25-40 ° C, and another adsorption method It is formed in the methanol or acetone solution of the cyanomethane complex in the matt state. Figure 11a shows [Ru (dcH2b) 2 (NCCH3) 2] 2+ complex (spectrum A) on the Zr02 film and Immersed in 0.1M tetrabutylammonium gasified (TBAC1) to observe the obtained spectrum change. Irradiating the film with an unfiltered 150W Xe lamp caused a rapid change from the initial spectrum (A) to the final spectrum (B). Spectral changes are consistent with the results of photo substitution of the coordinated cyanomethane with chlorine. The dried film was irradiated with light with a wavelength greater than 55 Onm. A step change in the spectrum. The time scale of the photo-substitution reaction is determined by the laser fast flash solution experiment. The methanol solution of [Ru (dcH2b) 2 (NCCH3) 2] 2+ complex in the presence of 0.1M TBAC1 uses ruby laser and Nd -YAG laser is irradiated with the excitation beam, and the beam is transmitted with a pulse of 2-5mJ plus a half width of 5-7ns. Figure 1 lb shows the laser excitation of [Ru (dcH2b) 2 (NCCH3) 2] 2 + + complex. Page 41 This standard applies the CNS A4 specification (21G X 297 mm) '" (Please read the precautions on the back before filling in this page> Order --------- line i Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economy 526488 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy A7 B7 V. Description of the invention (5) After the absorption peak center appeared at 50 nm, since CH3CN was replaced by chlorine (the part marked with B), the process was completed at a time scale of 50 ns. A similar reaction also occurred in tetrabutylamino NCS (TBANCS) in the presence of complexes, adsorbing [with 11 ((1 (: 11213) 2 ^ (:(: 113) 2] 2 ++ 21:02 films of complexes in 0.1M TBANCS and methanol at 150W Xe lamp irradiation, the spectral changes are consistent with the results of the formation of [Ru (dcH2b) 2 (NCS) 2] 2+. It is worth noting that the 'cyanoethane complex is converted to NCS-derivatives due to the elastic mode of the coordination NCS group. , Also accompanied by the emergence of the center of the radiation peak at 75 nm and the emergence of a strong infrared absorption band at 2 100 cm-1. Using "Ru (4,4, -bpyCH1P〇iH1) 1 (NCCHy1l2 + Preparation of Type I apparatus rRuH ^ -bpvCt ^ PC ^ HyyNCCHygl2. Preparation of the ligand 4,4'-ethoxycarbonyl-2,2'-piperidin border (1)

4,4’-二乙氧羰基-2,2’-二毗啶（5.0g，20.5 mmol)於 400mL純乙醇的懸浮液中加入5mL濃硫酸，混合物迴流 80分鐘以得到一澄清溶液並冷卻至室溫，加入40OmL水並於真空下移除多餘的乙醇，以NaOH調整pH值至中性並過滤及水洗（p Η = 7)沉殿物，此固體被乾燥而得到 5 · 5 g (9 0%)的（1)，其1H NMR 光譜（3 00 MHz，CDC13) 5ppmM.45 (6H, t，2CH2C//j)，4·46 (4H，q，2C//2CH3)，7.98 (2H，dd, 芳香族1*1在（：5及（：5’），8.88(211，（1，芳香族1^在（：6及（：6’）， 9.9〇 (2H，s，芳香族 H 在 C3 及 C3’），CUvHi6N2〇4 元素分析；計算 C 63.98，Η 5.37, N 9.33%，發現 C 63.43, Η 5.71，N 第42頁本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） -1 n n i n SMmmm I n I l_i a·— ·**0> w· mm w w w · w nw an·· am w . I (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（） 9.57%。 4.4、二（氫氧甲基）-2,2，-二呲啶（2) 4.4、二（氫氧甲基）-2,2、二呲啶（3〇g，1〇〇 20 0mL純乙醇的懸浮液中加入一部分8 2g硼氫化鈉，混合物迴流3小時並冷卻至室溫，然後加入2〇〇mL飽和氯化銨水溶液以分解多餘的氫化删，移除多餘的乙醇並將沉澱固體以最小量水溶解，此溶液以乙酸乙酯（5>< 200mL)萃取，然後以硫酸鈉及旋轉蒸發乾燥，無須進一步純化即得到可用1.7g(80<^產率）的固體（2)’其1HNMR光譜（300 MHz， CD3OD) δ ppm: 4.75 (4H，s，2CH2〇K), 7.43 (2H, q5 3Λ///=6Ηζ,芳香族 H 在 C5 及 C5’），8·25 (2H，s，芳香族 H 在 C)及 C3 )，9.00 (2H，d，芳香族 H[在 C6 及 C6 )，Ci2Hi2N202 元素分析：計算 C 66.65，Η 5.59, N 12.95%，發現 C 65.90, Η 5.70, N 12.32%。 4,4，-二（溴甲基）-2,2’-二吼啶（3) (2)之溶液（0.9g，4.2 mmol)溶於48%溴化氫及濃硫酸 (6·7mL)混合物中，產生的溶液迴流6小時並使其冷卻至室溫，然後加入40mL水，以NaOH調整pH值至中性並過濾及水洗沉澱物，利用空氣乾燥，將沉澱固體溶解於三氯甲烷（40mL)中，然後以硫酸鎂及蒸發乾燥，得到1.2g (85% 產率）的（3)為白色粉末，其1H NMR光譜（300 MHz，CDC13) 5 ppm: 4·50 (4H，s，2Cii2)，7.3 8 (2H，q，Vm=5Hz，芳香族 H 在 C5 及 C5’），8·45 (2H，d，芳香族 H 在 C3 及 C3’），8_68 (2H, d, 3Jhh^SUz,芳香族 H 在 C6 及 C6’），C12H1()N2Bi:2 第43頁本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公f ) ^--------^--------- (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）元素分析·计异 C 42.14，Η 2.95，N 6.19%，發現 c 42 03 Η 3.09, Ν 8.38% 〇 4,4’-二（二乙基甲基磷酸）-2,2、二说啶（4) (3)(1.5g，4·4 mmol)之三氯甲烷（10mL)溶液與15mL的三乙基亞鱗酸在氮氣中迴流3小時，在高真空中移除多餘的亞磷酸，然後利用矽膠管柱層析（洗提液：乙酸〇 §旨/甲醇 80/20)純化粗產物’得到1.6g(80%產率）的（4)，其1HNMR 光譜（300 MHz，CDCl3)5ppm: 1·29 (12H，t， 4POCH2C//3), 3.32 (4H, t, 2Jpch=z22Hz, 2CH2?)9 4.09 (6H, dq, 3Jp〇CH^7Hzy 3Jhh^7Uz9 4POC^2CH3), 7.35-7.38 (2H? m, 芳香族H在C5及C5’），8.34-8.3 7 (2H，m5芳香族H在C3 及 C3’），8·62 (2H，d，3J別=5Hz,芳香族 H 在 C6 及 C6’），其 31P NMR 光譜（CDCl3)5ppm: 25.37，C2〇H30N2〇6P2 元素分析：計算 C 52.63, H 6.63, N 6· 14%，發現 C 52.83, H 6.59, N 6.0 1 % 0 2,2’-二吡啶-4,4’-二甲基-二磷酸（5) 酉旨類（4)(100 mg，0.22 mmol)與18%氯化氫溶液（2mL) 加熱並迴流3小時，水溶性酸以旋轉蒸發，得到60 mg的酸（5)(80%產率），其1HNMR 光譜（300MHz，D2OpH = 7)5 ppm: 2·95 (4H，d，好=22Hz，2 C//2P)，7·35 (2H，d，芳香族11在<：5及（：5’），7.85(2^3，芳香族^1在（：3及0：3’），8.42 (2H，d，芳香族 H 在 C6 及 C6’），其 31P NMR 光譜（D20 pH = 7) <5 p p m: 1 7 · 3 5 ° 本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐） ----------- --------tr---------$·, ^ 产 (請先閱讀背面之注意事項再填寫本頁) 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）製備錯合物 [Ru((4,4，-(C2H5)2P03CH2)2bpy)2Rxi(NCCH3)2]2+(6) RM2D(80 mg, 0.38 mmol)與氯化經（1600 mg，38 111111〇1)之〇%?(35]111)在氬氣中加入配合基（5)(312 11^，0.68 mmol)之DMF(5ml)，1 20°C下將溶液加熱8小時，然後於真空中將溶劑移除，粗產物利用矽膠之管柱層折進行純化，並以甲醇作為沖提劑，得到124 mg(30%)的產物（6), 其於甲醇中之吸收光譜：Amax 359 nm及514nm。 [Ru((H2P03CH2)2bpy)2(NCCH3)2]2+ 錯合物（6)於氫氯酸中水解，對應的氰甲烷錯合物依上述相同步驟製備得[Ru(dcH2b)2(NCCH3)2]2+，錯合物 [Ru((H2P03CH2)2bpy)2(NCCH3)2]2+於可見光範圍之吸收光譜係由MLCT能帶所控制最大吸收值在454 nm。實驗結果氰甲烷錯合物之光取代反應藉由實驗得到進一步證實，其係由含有發色團4,4’-bpyCH2P〇3H2配合基相似物種取代 dcH2b，[Ru(4,4’-bpyCH2P03H2)2(NCCH3)2]2+，這些在 Ti02 或Zr〇2的透明薄膜上執行的實驗顯示一相似的光反應性，其傾向於與CP或NCS·離子產生光取代反應，更表示沉積物 [Ru(4,4’-bpyCH2P03H2)2(NCCH3)2]2+之穩定性，即使在無水的有機溶劑存在下。這項事實係由於磷酸根官能基具有強烈的親和力用以鍵結金屬氧化物、二氧化矽、氧化鋁，特別是具有 OH基表面的固體基材。第45頁本紙張尺度適用中國國家標準<CNS)A4規格（210 X 297公釐） ------------4^^--------訂---------線 I * (請先閱讀背面之注意事項再填寫本頁) 526488 A7 B7 五、發明說明（）物作為Type II裝罾製備（rHOOCpyRuWNHyrNC-no卜CN-RuWNHj^pyCOOHDW 依據文獻公開的方法製備H00CpyRun(NH3)4(S04)(C.A. Bignozzi, C. Paradisi, S. Roffia, F. Scandola. Inor^g. Chem. 2 7, 408 (198 8))，在室溫中將200mg錯合物溶於200mL的 1(T3M HC1中，使溶液保持在氬氣環境中則錯合物被鋅汞齊（zinc amalgam)還原，一個小時後，溶液被轉移至含有 33.5 mg NC-noi:-CN之第二反應器中並於氬氣中再攪拌5 小時，然後加入固體NH4PF6的使錯合物產生沉澱，過濾後以乙酸清洗。實驗結巢製備 1〇4m 的（[HOOCpyRi^iNHA-NC-nor-CN-Ri^CNHApyCOOH])4^ 溶於95 %甲醇與5 %聚乙晞说啶-苯乙埽聚合物溶液中（其中聚乙烯啦啶-苯乙烯聚合物中含有1 〇%苯乙婦），一聚合物固體包含金屬錯合物與聚乙晞吡啶-苯乙婦聚合物有溶液中沉積至透明玻璃上並風乾，將紅色透明聚合物固體暴露於可見光範圍之中，其係利用截止波長540 nm的全能 150瓦氙（Xe)燈光照射，然後再將固體利用未過濾的氙（Xe) 燈於UV範圍中照射，此錯合物於甲醇溶液中之光譜變化已描述於第1 2圖中，第1 3圖係描述觀察錯合物吸附於固體聚合物薄膜上之光譜變化。第461 本紙張尺度適用中國國家標準（CNS)A4規格（210< 297公釐） (請先閱讀背面之注意事項再填寫本頁) • 裝 ·1111111. 經濟部智慧財產局員工消費合作社印製 526488 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（）由第1 2圖及第1 3圖中可發現當可見光照射電荷轉移能帶時結合die* (RuH-nor)MLCT轉變並未產生任何顏色變化’而在UV範圍中照射則產生顏色變化，如此暗示著激發悲π-π *正菠二埽的總數產生可見光吸收能帶顯著的褪色，與正菠二缔被異構化為四環婦一致。此系統獨特地顯示兩π-π*與MLCT態，僅其中之一（上層π-π*態）具有光反應為電異構物，如此可能的結果為由正蔽二烯至四環缔之超快速異構化反應與態至較低層MLCT激發態之衰減反應競爭。負料可藉由在UV範圍照射此種薄膜而被紀錄在分子能階’而讀取資料的執行則藉由在傳輸模式使用波長大於 540nm的光，在此無正菠二晞部分光異構化反應發生。第14圖說明type Π裝置之功能，其中正菠二埽部分異構化為四環埽部分。作為Type III f罾 1 備 fdt-bpviCOOH^Ri^CNy2- [Ru(CN)6](TBA)4 及一化學計量的 4,4’-bpy(COOH)2 溶解於二甲基甲醯胺（DMF)中並迴流2小時，反應混合物利用尺寸排除層析法於LH20中純化以DMF為沖提劑，含有所要錯合物之紅-紫色部分被收集並旋轉蒸發之乾燥。製備[((K^PC^CHg^bpymuiCN：^2- 第47頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------------訂---------線 Γ ~» (請先閱讀背面之注意事項再填寫本頁) 526488 A7To a suspension of 4,4'-diethoxycarbonyl-2,2'-dipyridine (5.0 g, 20.5 mmol) in 400 mL of pure ethanol was added 5 mL of concentrated sulfuric acid, and the mixture was refluxed for 80 minutes to obtain a clear solution and cooled to At room temperature, add 40OmL of water and remove excess ethanol under vacuum. Adjust the pH to neutral with NaOH and filter and wash with water (p Η = 7). The solid is dried to obtain 5 · 5 g (9 (1), its 1H NMR spectrum (3 00 MHz, CDC13) 5ppmM.45 (6H, t, 2CH2C // j), 4.46 (4H, q, 2C // 2CH3), 7.98 (2H , Dd, aromatic 1 * 1 in (: 5 and (: 5 '), 8.88 (211, (1, aromatic 1 ^ in (: 6 and (: 6'), 9.9〇 (2H, s, aromatic H in C3 and C3 '), CUvHi6N2O4 elemental analysis; Calculated C 63.98, Η 5.37, N 9.33%, found C 63.43, Η 5.71, N Page 42 This paper standard applies Chinese National Standard (CNS) A4 specification (210 χ 297 mm) -1 nnin SMmmm I n I l_i a · — · ** 0 > w · mm www · w nw an ·· am w. I (Please read the precautions on the back before filling this page) 526488 Economy A7 B7 printed by the Ministry of Intellectual Property Bureau employee consumer cooperative 2. Description of the invention () 9.57%. 4.4. Di (hydroxylmethyl) -2,2, -dipyridine (2) 4.4, Di (hydroxylmethyl) -2,2, dipyridine (30 g To a suspension of 10020 pure ethanol was added a portion of 82 g of sodium borohydride. The mixture was refluxed for 3 hours and cooled to room temperature, and then 200 mL of a saturated ammonium chloride aqueous solution was added to decompose the excess hydrogen, and removed. Excess ethanol and dissolve the precipitated solid with a minimum amount of water. This solution was extracted with ethyl acetate (5 > < 200mL), and then dried with sodium sulfate and rotary evaporation. No further purification was needed to obtain 1.7g (80 < ^ product) (2) 'solid (2)' its 1HNMR spectrum (300 MHz, CD3OD) δ ppm: 4.75 (4H, s, 2CH2〇K), 7.43 (2H, q5 3Λ /// = 6Ηζ, aromatic H at C5 and C5 '), 8.25 (2H, s, aromatic H in C) and C3), 9.00 (2H, d, aromatic H [in C6 and C6), Ci2Hi2N202 Elemental analysis: Calculate C 66.65, 59 5.59, N 12.95 %, Found C 65.90, Η 5.70, N 12.32%. A solution of 4,4, -bis (bromomethyl) -2,2'-dimethylaridine (3) (2) (0.9 g, 4.2 mmol) in 48% hydrogen bromide and concentrated sulfuric acid (6.7 mL) In the mixture, the resulting solution was refluxed for 6 hours and allowed to cool to room temperature, then 40 mL of water was added, the pH was adjusted to neutrality with NaOH, and the precipitate was filtered and washed with water, dried with air, and the precipitated solid was dissolved in chloroform ( 40mL), and then dried with magnesium sulfate and evaporation to obtain 1.2g (85% yield) of (3) as a white powder, whose 1H NMR spectrum (300 MHz, CDC13) 5 ppm: 4 · 50 (4H, s, 2Cii2), 7.38 (2H, q, Vm = 5Hz, aromatic H at C5 and C5 '), 8.45 (2H, d, aromatic H at C3 and C3'), 8_68 (2H, d, 3Jhh ^ SUz, aromatic H at C6 and C6 '), C12H1 () N2Bi: 2 page 43 This paper is applicable to China National Standard (CNS) A4 (210 x 297 male f) ^ -------- ^ --------- (Please read the notes on the back before filling out this page) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Elemental analysis and differentiating C 42.14, Η 2.95, N 6.19%, found c 42 03 Η 3.09, Ν 8.38% 〇4,4'-bis (diethylmethylphosphoric acid) -2,2, bispyridine (4) (3) (1.5g, 4.4 mmol) solution of trichloromethane (10mL) and 15mL of trichloromethane Ethylphosphonic acid was refluxed under nitrogen for 3 hours, and excess phosphorous acid was removed in high vacuum, and then the crude product was purified by silica gel column chromatography (eluent: acetic acid 〇 § / methanol 80/20) to obtain 1.6g (80% yield) of (4), whose 1HNMR spectrum (300 MHz, CDCl3) 5ppm: 1.29 (12H, t, 4POCH2C // 3), 3.32 (4H, t, 2Jpch = z22Hz, 2CH2? ) 9 4.09 (6H, dq, 3Jp〇CH ^ 7Hzy 3Jhh ^ 7Uz9 4POC ^ 2CH3), 7.35-7.38 (2H? M, aromatic H at C5 and C5 '), 8.34-8.3 7 (2H, m5 aromatic H At C3 and C3 '), 8.62 (2H, d, 3J, 5Hz, aromatic H at C6 and C6'), its 31P NMR spectrum (CDCl3) 5ppm: 25.37, C2OH30N2O6P2 Elemental analysis: calculation C 52.63, H 6.63, N 6.14%, C 52.83, H 6.59, N 6.0 1% 0 2,2'-dipyridine-4,4'-dimethyl-diphosphate (5) 4) (100 mg, 0.22 mmol) and 18% hydrogen chloride solution (2 mL) were heated and refluxed for 3 hours, and the water-soluble acid was subjected to rotary evaporation to obtain 60 mg of acid (5) (80% yield) , Its 1HNMR spectrum (300MHz, D2OpH = 7) 5 ppm: 2.95 (4H, d, good = 22Hz, 2 C // 2P), 7.35 (2H, d, aromatic 11 at <: 5 and (: 5 '), 7.85 (2 ^ 3, aromatic ^ 1 at (: 3 and 0: 3'), 8.42 (2H, d, aromatic H at C6 and C6 '), and its 31P NMR spectrum (D20 pH = 7) < 5 ppm: 1 7 · 3 5 ° This paper size applies to Chinese National Standard < CNS) A4 specification (210 X 297 mm) ----------- ----- --- tr --------- $ ·, ^ property (please read the notes on the back before filling out this page) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention () Preparation of the complex [Ru ((4,4,-(C2H5) 2P03CH2) 2bpy) 2Rxi (NCCH3) 2] 2+ (6) RM2D (80 mg, 0.38 mmol) and chlorination via (1600 mg, 38 111111. 1) 0%? (35) 111) Add DMF (5ml) of the complex (5) (312 11 ^, 0.68 mmol) in argon, heat the solution for 8 hours at 120 ° C, and then vacuum The solvent was removed, and the crude product was purified by silica gel column layer folding, and methanol was used as the eluent to obtain 124 mg (30%) of the product (6). Its absorption spectrum in methanol: Amax 35 9 nm and 514nm. [Ru ((H2P03CH2) 2bpy) 2 (NCCH3) 2] 2+ complex (6) was hydrolyzed in hydrochloric acid, and the corresponding cyanomethane complex was prepared in the same way as above. [Ru (dcH2b) 2 (NCCH3 ) 2] 2+, the complex [Ru ((H2P03CH2) 2bpy) 2 (NCCH3) 2] 2+ in the visible light absorption spectrum is controlled by the MLCT band and the maximum absorption value is 454 nm. Experimental results The photosubstitution reaction of the cyanomethane complex was further confirmed by experiments. It was replaced by dcH2b with a similar species containing a chromophore 4,4'-bpyCH2P〇3H2, [Ru (4,4'-bpyCH2P03H2) 2 (NCCH3) 2] 2+, these experiments performed on a transparent film of Ti02 or Zr〇2 show a similar photoreactivity, which tends to produce a photo-replacement reaction with CP or NCS · ions, and it also represents the sediment [ The stability of Ru (4,4'-bpyCH2P03H2) 2 (NCCH3) 2] 2+, even in the presence of anhydrous organic solvents. This fact is due to the strong affinity of phosphate functional groups for bonding metal oxides, silica, alumina, and especially solid substrates with OH-based surfaces. Page 45 This paper size applies Chinese National Standard < CNS) A4 specification (210 X 297 mm) ------------ 4 ^^ -------- Order --- ------ Line I * (Please read the notes on the back before filling this page) 526488 A7 B7 V. Description of invention () The product is prepared as Type II decoration (rHOOCpyRuWNHyrNC-nobu CN-RuWNHj ^ pyCOOHDW According to the literature Published method: H00CpyRun (NH3) 4 (S04) (CA Bignozzi, C. Paradisi, S. Roffia, F. Scandola. Inor ^ g. Chem. 2 7, 408 (198 8)), 200 mg at room temperature The complex was dissolved in 200 mL of 1 (T3M HC1, and the solution was kept in an argon atmosphere, and the complex was reduced by zinc amalgam. After one hour, the solution was transferred to a solution containing 33.5 mg NC-noi: -CN in the second reactor and stirred for another 5 hours in argon, and then added solid NH4PF6 to precipitate the complex, filtered and washed with acetic acid. Experiments were performed to prepare 104 m of [[HOOCpyRi ^ iNHA- NC-nor-CN-Ri ^ CNHApyCOOH]) 4 ^ Dissolved in 95% methanol and 5% polyethylene glycol-phenylethylfluorene polymer solution (including polyvinyl pyridine-styrene polymer containing 10% Acetophenone), a polymerization The solid contains a metal complex and polyacetopyridine-phenethyl polymer. The solution is deposited on a transparent glass and air-dried. The red transparent polymer solid is exposed to the visible light range. It uses the full power of the cut-off wavelength of 540 nm. 150W xenon (Xe) light was irradiated, and then the solid was irradiated in the UV range with an unfiltered xenon (Xe) lamp. The spectral change of this complex in a methanol solution has been described in Figure 12 and Figure 1. Figure 3 describes the spectral changes observed when the complex is adsorbed on the solid polymer film. The 461th paper size applies the Chinese National Standard (CNS) A4 specification (210 < 297 mm) (Please read the precautions on the back before filling (This page) • Equipment · 1111111. Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 526488 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention When visible light is irradiated with the charge transfer energy band, the combination of die * (RuH-nor) MLCT transformation does not produce any color change ', but irradiation in the UV range produces a color change, which implies that the sad π-π * positive Generating two broom total visible absorption band of significant fading, positive association was isomerized spinach two women tetracyclic consistent. This system uniquely shows two π-π * and MLCT states, and only one of them (the upper π-π * state) has a photoreaction as an electric isomer, so the possible result is that from the positive diene to the tetracyclic association The ultra-fast isomerization reaction competes with the decay of the excited state to the lower MLCT excited state. The negative material can be recorded at the molecular energy level by irradiating such a thin film in the UV range, and the reading of the data is performed by using light with a wavelength greater than 540 nm in the transmission mode. Chemical reaction takes place. Figure 14 illustrates the function of a type Π device in which the ortho-difluorene moiety isomerizes into a tetracyclic hydrazone moiety. As Type III f 罾 1, fdt-bpviCOOH ^ Ri ^ CNy2- [Ru (CN) 6] (TBA) 4 and a stoichiometric amount of 4,4'-bpy (COOH) 2 were dissolved in dimethylformamide ( DMF) and reflux for 2 hours. The reaction mixture was purified in LH20 using size exclusion chromatography with DMF as the eluent. The red-purple portion containing the desired complex was collected and dried by rotary evaporation. Preparation [((K ^ PC ^ CHg ^ bpymuiCN: ^ 2- page 47) This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ------------- ------- Order --------- Line Γ ~ »(Please read the notes on the back before filling this page) 526488 A7

五、發明說明（）利用如上述相同之方法，除了化學計量的七4 bpy(COOH)2 以（H2P03CH2)2bpy 取代。 (請先閲讀背面之注意事項再填寫本頁) 實驗結果此二錯合物顯現明顯的媒合顯色現象且顯出IR光譜類似已描述於[(bPy)Ru(CN)4]4·錯合物之光譜（c.j· Timps〇n，c.A.5. Description of the invention () Using the same method as above, except that the stoichiometric amount of 7 bpy (COOH) 2 is replaced with (H2P03CH2) 2bpy. (Please read the precautions on the back before filling in this page) Experimental results The two complexes show obvious color matching phenomenon and IR spectrum similar to that described in [(bPy) Ru (CN) 4] 4. Spectroscopy of Compounds (cj · Timpson, cA

Bignozzi，B.P. Sullivan，E.D· Kober，T.J. Meyer J. Phys.Bignozzi, B.P. Sullivan, E.D. Kober, T.J. Meyer J. Phys.

Chem· 100, 291 5 (1996))，（TBA)2[Ru(dcb)2(CN)4]錯合物鹽落於甲醇落液中顯示MLCT吸收能帶之最大吸收值在355 及465nm，甲醇溶液中之錯合物亦放射，具有最大放射值在690nm及73 ns之生命週期。經濟部智慧財產局員工消費合作社印製第15圖用以說明Type III裝置之功能，其中一分子感光劑與電子接收劑被吸附於二氧化鈥基材上，第1 6圖描述觀察透明二氧化鈦薄膜已吸附Ru(dcb)2(bpy)(充當（S))及與雙核的 K[trans-HOOCpyRum(NH3)4-NCRun(CN)5]錯合物（充當 (Q))以150W氙（Xe)燈照射之光譜變化，吸附於Ti02上係由兩物種於甲醇中之2X 1 (Γ4Μ溶液所完成，最終光譜特性維持在持續照光之下，原始光譜可在黑暗或陰影底下重新建立，類似的特性亦發生於[(4,4’-bpy(COOH)2Ru(CN)4]2·、 [(4,4，- (H2P03CH2)2bpyRu(CN)4]及[(4,4’-bpy(COOH)2Re(CO)3]，其中L是Cl·、CN-或毗啶，雖然取代基較佳位置為鍵結在 4,4’位置以得到最大偶極矩，然而其他位置如3,3’及5,5’亦可接受β 上述說明與實例揭示本發明之許多方法及材料，本發第48頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Chem. 100, 291 5 (1996)), (TBA) 2 [Ru (dcb) 2 (CN) 4] complex salt in methanol, the maximum absorption value of MLCT absorption band is 355 and 465nm, The complex in the methanol solution is also radiated, with a maximum emission value of 690 nm and a life cycle of 73 ns. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed Figure 15 to illustrate the function of the Type III device, in which a molecule of photosensitizer and electron-receiving agent is adsorbed on the substrate of dioxide, and Figure 16 depicts the observation of transparent titanium dioxide film Has adsorbed Ru (dcb) 2 (bpy) (acting as (S)) and K [trans-HOOCpyRum (NH3) 4-NCRun (CN) 5] complex (acting as (Q)) with 150W xenon (Xe ) The change in the spectrum of the lamp irradiation. The adsorption on Ti02 is completed by the 2X 1 (Γ4M solution of the two species in methanol. The final spectral characteristics are maintained under continuous light. The original spectrum can be re-established in the dark or shadow. Characteristics also occur in [(4,4'-bpy (COOH) 2Ru (CN) 4] 2 ·, [(4,4,-(H2P03CH2) 2bpyRu (CN) 4], and [(4,4'-bpy ( COOH) 2Re (CO) 3], where L is Cl ·, CN-, or pyridine. Although the preferred position of the substituent is the bond at 4,4 'to obtain the maximum dipole moment, other positions such as 3,3 'And 5,5' are also acceptable. Β The above description and examples reveal many methods and materials of the present invention. The paper size on page 48 of this issue applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm).

526488 五、發明說明（）明容許在方法及材料上之改變，其他製造方法戒装f亦< 仃，於熟悉此項技術者而言在參閱本發明所揭系之内谷後可輕易得知此些變更，因此，本發明所揭示之實施例僅用於說明非用以限定本發明之實施，其他更動或潤飾皆包含於以下本發明所請申請專利範圍之精神與領域中。 -------------------訂---------線 (請先聞讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製育 49 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）526488 V. Description of the invention () It is stated that changes in methods and materials are allowed. Other manufacturing methods or installations are also <仃, which can be easily obtained by those skilled in the art after referring to the inner valley disclosed by the present invention. Knowing these changes, the embodiments disclosed in the present invention are only used to illustrate the implementation of the present invention, and other modifications or retouching are included in the spirit and field of the patent application scope of the present invention. ------------------- Order --------- line (please read the precautions on the back before filling out this page) Staff of Intellectual Property Bureau of Ministry of Economic Affairs Printed by Consumer Cooperatives 49 This paper is sized for China National Standard (CNS) A4 (210 X 297 mm)

Claims

526488 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 六、申請專利範圍 1· 一種二元資料記錄媒介，其至少包含·· 一基材；一記錄層於基材上，該記錄層包含一有機金屬的過渡金屬錯合物，該過渡金屬錯合物吸收第—波長的光；其中該過渡金屬錯合物具有一光感應激發態，該光感應激發態結果產生一反應產物於記錄層，其唆收第二波長的光’該第一以及第二波長不同，且該第一波長的光吸收值定為第一數值，而該第二波長的光吸收值定為第二數值，第一數值及第二數值對應為二元碼。 2 ·如申請專利範圍第1項所述之二元資料記錄媒介，其中上述之過渡金屬錯合物包含至少下列分子式之一： [M(N-N)2L2]n [M(N-N)L4]n [M(N-N-N)L3]n 及 [M(N-N-N)2]n 其中Μ為一過渡金屬； Ν-Ν為發色團的聚说啶配合基結合選自下列群組之一至二個取代基包含：-COOH、-Β(ΟΗ)2、-Ρ〇3Η2 及-R-ΡΟ3Η2，其中R為一飽和或一芳香碳氫化合物； Ν-Ν-Ν為發色團的三说啶配合基結合選自下列群組之一至三個取代基包含：-€0011、-8(01'1)2、-?〇3112、-1^-Ρ 0 3 Η 2及苯基，其中苯基結合一個或更多個選自下列群組第50頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) 一 C請先閲讀背面之注意事項再填寫本頁) ·_ 訂-------- ΛΙ01--------------- 526488 A8 B8 C8526488 Printed by A8 B8 C8 D8 of Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application scope of patent 1. A binary data recording medium including at least a substrate; a recording layer on the substrate, the recording layer contains An organometallic transition metal complex that absorbs light at the first wavelength; wherein the transition metal complex has a light-induced excited state that results in a reaction product in the recording layer It absorbs light of a second wavelength. The first and second wavelengths are different, and the light absorption value of the first wavelength is set to a first value, and the light absorption value of the second wavelength is set to a second value. A value and a second value correspond to a binary code. 2 · The binary data recording medium according to item 1 of the scope of patent application, wherein the transition metal complex described above contains at least one of the following molecular formulas: [M (NN) 2L2] n [M (NN) L4] n [ M (NNN) L3] n and [M (NNN) 2] n where M is a transition metal; N-N is a polyordinyl ligand group which is a chromophore combined with one or two substituents selected from the group consisting of: -COOH, -Β (ΟΗ) 2, -PO3Η2, and -R-PO3Η2, where R is a saturated or an aromatic hydrocarbon; NR-N-N is a tris-pyridine complexing group of a chromophore selected from One to three substituents in the following groups include:-€ 0011, -8 (01'1) 2,-? 3111, -1 ^ -P 0 3 Η 2 and phenyl, wherein phenyl is bonded to one or more One is selected from the following group. Page 50 This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) One C, please read the precautions on the back before filling in this page) · _ Order ----- --- ΛΙ01 --------------- 526488 A8 B8 C8

經濟部智慧財產局員工消費合作社印製六、申請專利範圍取代基包含：-COOH、-B(〇H)2、-p〇3H2 及-R-P〇3H2，其中R為一飽和或一芳香碳氫化合物；及 L為非發色團的單齒或多齒附屬配合基。 J •如申請專利範圍第2項所述之二元資料記綠媒介，其中上述之Μ係選自鈷、鎳、銅、銥、鈀、鉑、鍊、，锇、鐵、釕及铑。 4 ·如申請專利範圍第2項所述之二元資料記錄媒介，其中上述之Ν-Ν係選自取代與未取代的2，2 ’ -二4症基、取代與未取代的1，1 〇 -二氮雜菲以及取代或未取代的2，2 ’ -二喧琳° 5.如申請專利範圍第2項所述之二元資料記錄媒介，其中上述之Ν-Ν-Ν係被苯基取代，且其中該苯基結合一取代基於對位上。 6.如申請專利範圍第2項所述之二元資料記錄媒介，其中上述之 L 係選自 NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、NCS、N3·、-CH3·、Η、草酸基、C0、CN·、 NO、H20、OFT、NH3、***、呲啶、對二氮雜苯、4,4、二吡啶、4,4、二吡啶基乙烷、4,4、二吡啶基乙缔、4-氰吡淀、二苯甲腈、對二氮己環、no2_及乙酿丙酮。第51頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） wav a··· WM MM w· aw I MM 蜃 ·* I 一 a n n n Mmmmm fli ϋ l I I t - (請先閱讀背面之注意事項再填寫本頁) 526488 A8 B8 C8 D8 六、申請專利範圍 (請先閱讀背面之注意事項再填寫本頁) 7. 如申請專利範圍第2項所述之二元資料記錄媒介，其中上述之L包含一配位溶劑選自下列族群包含：乙醯丙酮、甲醇、氰甲烷、丙酮、四氫呋喃、乙醇、二甲基甲醯胺及二甲基氧硫基。 8. 如申請專利範圍第1項所述之二元資料記錄媒介，其中上述之基材選自下列族群包含非晶形、微結晶或半導 9. 如申請專利範圍第1項所述之二元資料記錄媒介，其中上述之過渡金屬錯合物包含至少下列分子式之一： [M(N-N)2(Y-nor-Y)(L)]n [M(N-N)2(Y-nor-Y)2]n [M(N-N)2(X)(Y-nor-Y)M(N-N)2(L)]n [M(N-N-N)(Y-nor-Y)(L)2]n [M(N-N-N)2(Y-nor-Y)2(L)]n 及 [M(N-N-N)2(L)2(Y-nor-Y)M(N-N-N)2(L)2]n 經濟部智慧財產局員工消費合作社印製其中Y係選自下列群組包食氰基、吡啶以及吡啶亞甲基，而nor為正疲二埽； Μ為過渡金屬； Ν-Ν為取代或未取代的發色團聚说啶配合基； Ν-Ν-Ν為取代或未取代的發色團三毗啶配合基； L為非發色團的單齒或多齒附屬配合基；及第52頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 526488 A8 B8 C8 D8 六、申請專利範圍 X為一配合基係選自下列族群之一包含聚氮雜大環族及聚硫代大環族。 10.如申請專利範圍第1項所述之二元資料記錄媒介，其中上述之過渡金屬錯合物以至少下列分子式之一表示： [trans-HOOCpyRun(X)4-NC-nor-CN]2+ , {[trans-HOOCpyRun(X)4-NC]2-nor}4+ [trans-CH3-OOCpyRun(X)4-NC-nor-CN]2+ {[trans-CH3-OOCpyRun(X)4-NC]2-nor]4+ [trans-CH3CH2-〇〇CpyRuII(X)4-NC-iior-CN]2+ 及 {[trans-CH3CH2-OOCpyRun(X)4-NC]2-nor]4+ 其中HOOCpy為異菸鹼酸；NC-nor-CN為二氰正菠二婦配合基； X係選自下列群組包含聚氮雜大環族、聚硫代大環族及 NH3 ; trans為以釕（Ru)為中心之結構。 1 1.如申請專利範圍第1項所述之二元資料記錄媒介，其中上述之基材為一半導體，以及該過渡金屬錯合物包含一分子感光劑以至少下列分子式之一表示： [M(N-N)2L2]n [M(N-N)L4]n [M(N-N-N)L3]n 及 [M(N-N-N)2]n 第53頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 · II ϋ ϋ n n n n I n n n n i ml l I I -ϋ I— 1 n i n 1 n n n ·ϋ 526488 A8 B8 C8 D8Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6. The scope of patent application includes substituents: -COOH, -B (〇H) 2, -p〇3H2 and -RP〇3H2, where R is a saturated or an aromatic hydrocarbon A compound; and L is a non-chromophore monodentate or multidentate accessory ligand. J • The binary data recording green medium as described in item 2 of the scope of the patent application, wherein the above-mentioned M is selected from the group consisting of cobalt, nickel, copper, iridium, palladium, platinum, chain, osmium, iron, ruthenium, and rhodium. 4 · The binary data recording medium as described in item 2 of the scope of the patent application, wherein the above N-N is selected from the group consisting of substituted and unsubstituted 2,2′-bis-4 groups, substituted and unsubstituted 1,1 〇-Diazaphenanthrene and substituted or unsubstituted 2,2'-dioxine. 5. The binary data recording medium as described in item 2 of the scope of patent application, wherein the above-mentioned N-N-N is benzene Group substitution, and wherein the phenyl group is bonded to a substitution based on the para position. 6. The binary data recording medium as described in item 2 of the scope of patent application, wherein the above-mentioned L is selected from NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4- CN, halo, NCS, N3 ·, -CH3 ·, hydrazone, oxalate, C0, CN ·, NO, H20, OFT, NH3, triazole, pyridine, p-diazabenzene, 4, 4, dipyridine , 4,4, dipyridylethane, 4,4, dipyridylethylene, 4-cyanopyridine, dibenzonitrile, p-diazepine, no2_ and ethyl acetone. Page 51 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 public love) wav a ··· WM MM w · aw I MM 蜃 · * I 一 annn Mmmmm fli ϋ l II t-(please Read the notes on the back and then fill out this page) 526488 A8 B8 C8 D8 6. Scope of patent application (please read the notes on the back before filling out this page) 7. Binary data recording medium as described in item 2 of the scope of patent application Wherein, the above-mentioned L comprises a coordination solvent selected from the following groups including: acetamidine, methanol, cyanomethane, acetone, tetrahydrofuran, ethanol, dimethylformamide and dimethyloxythio. 8. The binary data recording medium as described in item 1 of the scope of patent application, wherein the above-mentioned substrate is selected from the following groups including amorphous, microcrystalline or semiconducting 9. The binary as described in item 1 of the scope of patent application Data recording medium, wherein the transition metal complex described above contains at least one of the following molecular formulas: [M (NN) 2 (Y-nor-Y) (L)] n [M (NN) 2 (Y-nor-Y) 2] n [M (NN) 2 (X) (Y-nor-Y) M (NN) 2 (L)] n [M (NNN) (Y-nor-Y) (L) 2] n [M ( NNN) 2 (Y-nor-Y) 2 (L)] n and [M (NNN) 2 (L) 2 (Y-nor-Y) M (NNN) 2 (L) 2] n Intellectual Property Office, Ministry of Economic Affairs Printed by the employee consumer cooperative, where Y is selected from the group consisting of cyano, pyridine, and pyridyl methylene, and nor is dioxin; M is a transition metal; Ν-Ν is a substituted or unsubstituted chromogenic reunion Said pyridine complex; Ν-Ν-Ν is a substituted or unsubstituted chromophore tripyridine complex; L is a non-chromophore monodentate or multidentate accessory complex; and page 52 of this paper applies to China National Standard (CNS) A4 specification (210 X 297 mm) 526488 A8 B8 C8 D8 6. The scope of patent application X is a coordination group selected from the following groups Macrocyclic group comprising polyethylene and poly-macrocyclic aromatic thio. 10. The binary data recording medium according to item 1 of the scope of patent application, wherein the transition metal complex is represented by at least one of the following molecular formulas: [trans-HOOCpyRun (X) 4-NC-nor-CN] 2 +, {[trans-HOOCpyRun (X) 4-NC] 2-nor} 4+ [trans-CH3-OOCpyRun (X) 4-NC-nor-CN] 2+ {[trans-CH3-OOCpyRun (X) 4 -NC] 2-nor] 4+ [trans-CH3CH2-〇〇CpyRuII (X) 4-NC-iior-CN] 2+ and {[trans-CH3CH2-OOCpyRun (X) 4-NC] 2-nor] 4 + Where HOOCpy is isonicotinic acid; NC-nor-CN is dicyano-n-spinate; and X is selected from the group consisting of polyaza macrocycles, polythiomacrocycles, and NH3; trans is Structure centered on ruthenium (Ru). 1 1. The binary data recording medium according to item 1 of the scope of patent application, wherein the above-mentioned substrate is a semiconductor, and the transition metal complex contains a molecular photosensitizer expressed by at least one of the following molecular formulas: [M (NN) 2L2] n [M (NN) L4] n [M (NNN) L3] n and [M (NNN) 2] n page 53) This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 Mm) (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · II II ϋ nnnn I nnnni ml l II -ϋ I— 1 nin 1 nnn · 526488 A8 B8 C8 D8

經濟部智慧財產局員工消費合作社印制衣六、申請專利範圍 Μ為一過渡金屬； Ν-Ν為發色團的聚ττ比淀配合基及結合選自下歹,彳群^ 之一至二個取代基包含：-COOH、-Β(0Η)2、-ρ〇 Η J 1:12 及. R-PO3H2’其中R為一飽和或一芳香碳氫化合物； N-N-N為發色團的三吡啶配合基結合選自下歹彳砰組之一至三個取代基包含：-COOH、-B(0H)2、-Ρ(χ3Η2、 r Ρ03Η2及苯基，其中該苯基結合一個或更多個選自严F列群組取代基包含：-COOH、-B(0H)2、-Ρ03Η2 及-R-P〇3H 其中R為一飽和或一芳香碳氫化合物； L為非發色團的單齒或多齒附屬配合基；及其中該分子感光劑具有一光吸收光譜及能夠射出— 電子進入基材空的傳導帶，在可見光吸收值上，以形成氧化分子感光劑，其具有一光吸收光譜不同於未氧化分子感光劑’其中顯現一電子接收劑具有一光吸收光譜及能夠由一具有不同的光吸收光譜之還原電子接收劑接受電子，其中該氧化分子感光劑及該還原分子感光劑之間電荷分離維持在持續照射可見光。 1 2 ·如申請專利範圍第1 1項所述之二元資料記錄媒介，其中上述之基材選自下列族群包含三氧化鎢、二氧化欽、二氧化鋅及二氧化錫。 13·如申請專利範圍第π項所述之二元資料記錄媒介，其中上述之基材為微結晶。第54頁 --------------擎---------- 丨訂ί t n ί «1 a— 1 I f蠓·-------------------- f請先閱讀背面之注意事項再填寫本頁} 526488 A8 B8 C8 D8 六、申請專利範圍 1 4.如申請專利範圍第1 1項所述之二元資料記錄媒介，其中上述之半導體基材包含膠體形式之微粒。 1 5 .如申請專利範圍第11項所述之二元資料記錄媒介，其中上述之微粒具有一平均直徑範圍由約1 Ο ηπι至約50 1 6 ·如申請專利範圍第1 1項所述之二元資料記錄媒介，其中上述之電子接收劑係由下列分子式之一表示： L，Printed clothing by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of the patent application M is a transition metal; NR-N is a poly ττ bidian complex with a chromophore and the combination is selected from one to two of the following groups: Substituents include: -COOH, -B (0Η) 2, -ρ〇Η J 1:12 and. R-PO3H2 'where R is a saturated or an aromatic hydrocarbon; NNN is a tripyridine complex of a chromophore The combination is selected from one to three substituents selected from the group consisting of: -COOH, -B (0H) 2, -P (χ3Η2, r P03Η2, and phenyl, wherein the phenyl group binds one or more selected from the group consisting of The group F substituents include: -COOH, -B (0H) 2, -P03Η2, and -RP〇3H where R is a saturated or an aromatic hydrocarbon; L is a non-chromophore monodentate or multidentate appendage Ligands; and the molecular photosensitizer has a light absorption spectrum and can be emitted-electrons enter the empty conduction band of the substrate, in the visible light absorption value to form an oxidized molecular photosensitizer, which has a light absorption spectrum different from unoxidized Molecular photosensitizers' in which an electron-receiving agent has a light absorption spectrum and Reduced electron receivers with different light absorption spectra accept electrons, wherein the charge separation between the oxidized molecular sensitizer and the reduced molecular sensitizer is maintained under continuous exposure to visible light. 1 2 · As described in item 11 of the scope of patent application A binary data recording medium, wherein the above-mentioned substrate is selected from the group consisting of tungsten trioxide, ammonium dioxide, zinc dioxide, and tin dioxide. 13. A binary data recording medium as described in item π of the scope of patent application, The above-mentioned substrate is microcrystalline. Page 54 -------------- Engine ---------- 丨 Order tl tn ί «1 a— 1 I f 蠓· -------------------- f Please read the notes on the back before filling out this page} 526488 A8 B8 C8 D8 VI. Application for patent scope 1 4. If applying for patent The binary data recording medium according to item 11 of the scope, wherein the above-mentioned semiconductor substrate contains particles in the form of colloids. 1 5. The binary data recording medium according to item 11 of the scope of patent application, wherein the above-mentioned particles have An average diameter range from about 10 ηπι to about 50 1 6 · Binary data as described in item 11 of the patent application range Recording medium, wherein the above-described electron-accepting agent system represented by one of the following formula: L,

(請先閱讀背面之注意事項再填寫本頁) # 經濟部智慧財產局員工消費合作社印製其中 Α為说啶結合對位之取代基係部分選自下列群組包含·· -COOH、-B(0H)2、-Ρ03Η2 及-R-P03H2，其中 R 為碳氮連結基； B為橋接配合基； - L ’，可相同或不同，其係選自下列群組之一配合基包含：NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、 NCS·、草酸基、CO、CN.、NO、毗啶、4-氰毗啶、二苯甲睛、H20、OH·、NH3、對二氮己環、Ν02·、被一個或更多個甲基取代或未取代的 2,2’-二毗啶基及被一個或更多個甲基取代與未取代的Μ0-二氮雜菲；及 Μ ’，可相同或不同，其係一過渡金屬能夠邊行氧化態第55頁一^J· ϋ I I tm— n ϋ n I n n I n n n ϋ ϋ n n n n n 1· I ϋ I n ϋ ϋ «I n I 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 526488 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 D8 六、申請專利範圍可逆的變化。 17 ·如申明專利範圍第11項所述之二元資料記錄媒介，額外地包含一薄的透明聚合物的薄膜，其中該薄膜係位於該έ己綠層之上。蜂 18.種储存資料為光學可讀取形式之方法，其包含： (I) 提供一光致變色金屬錯合物於一基材上，該光致變色錯合物吸收第一波長可見光； (II) 將該基材及附著的光致變色錯合物浸入含有配位化合物的液體中； (iu) 於選定的範圍照射附著於該基材的光致變色金屬錯合物以引發一光反應於該金屬錯合物與該配位化合物之間’結果反應產生一反應產物於該基材上，其吸收第二波長光，該第一及第二波長係選用於對應為資料儲存之二元碼；及 (iv) 移除多餘的配位化合物以使反應為不可逆的。 1 9. 一種使儲存於光學可讀取形式的資料回復之方法，其包含： (i) 提供一光學資料儲存媒介包含一金屬錯合物於一基材上，其中該金屬錯合物以一原始態及一反應態存在，該原始態具有一吸收或放射光譜不同於該反應態之光譜，其中金屬錯合物於原始態之範圍對應一二元數值丨或第56頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) Φ 經濟部智慧財產局員工消費合作社印製 526488 A8 B8 一- C8 ------- D8 ____ 六、申請專利範圍二坡長可見光；及 (Π)於選定的範圍照射該未氧化的分子感光劑，以引發一電子射入該基材空的導電帶，接著由該電子接收劑接收該電子，因而形成一氧化的分子感光劑，該氧化的分子感光劑吸收第三波長的光，因而形成還原的電子接收劑，該還原的電子接收劑吸收第四波長的光，該第三及第四波長組合被選用於對應為資料儲存之二元碼。 22· 一種使儲存於光學可讀取形式的資料回復之方法，其包含： (1) 提供一光學資料儲存媒介包含一分子感光劑及一電子接收劑吸附於一寬能隙的半導體基材上，其中該媒介的一個或更多個區域為氧化的分子感光劑或還原的電子接收劑，其中該氧化的分子感光劑具有一吸收或放射光譜不同於未氧化形式的分子感光劑的光譜，其中該還原的電子接收劑具有一吸收或放射光譜不同於未還原的電子接收劑的光譜，其中該氧化分子感光劑的範圍與該還原電子接收劑的範圍對應為二元數值丨或〇，且其中該分子感光劑未氧化態的範圍與該還原電子接收劑未還原態的範圍對應為相反的二元數值；其中該分子感光劑以下列分子式之一表示： [M(N-N)2L2]n [M(N-N)L4]n [M(N-N-N)L3]n 第58頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------^---------^ —^1. 餐 * (請先閱讀背面之注意事項再填寫本頁) A8 B8 C8 D8 526488 六、申請專利範圍及 [M(N-N-N)2]n 其中Μ為一過渡金屬具有一氧化態； Ν-Ν為發色團的聚ρ比啶配合基具有一電荷及結合選自下列群組之一至二個取代基包含：-COOH、-Β(〇η)2、_ ΡΟ3Η2及-R-P〇sH2，其中R為一飽和或一芳香碳4氣基； N-N-N為發色團的三毗啶配合基具有一電荷及結合選自下列群組之一至三個取代基包含：-COOH、-B(〇H)2、 -PChH2、-R-POsH2及苯基，其中該苯基結合一個或更多個選自下列群組取代基包含：-COOH、-B(OH)2、-P〇3h2及 -R-P03H2，其中R為一飽和或一芳香碳氫基； L為非發色團的單齒或多齒附屬配合基具有一電荷；及 η為總電荷數包含Μ氧化態及配合基電荷的代數總和； (ii) 反射一光束偏離該媒介，其中該光束具有一波長選擇性地被該氧化分子感光劑或該未氧化態分子感光劑之一所吸收；及 (iii) 於該光束被該媒介反射之後偵測光束強度，其中該被反射的光束強度顯示該光束係穿透氧化分子感光劑與還原電子接收劑的範圍或未氧化態分子感光劑與未還原態電子接收劑的範圍，因而將儲存於記錄媒介的二元數值回復。第59頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---------------------訂---------據翰 > (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 526488 A8 B8 C8 D8 六、申請專利範圍有不同光吸收光譜的氧化分子感光劑，其中該電子接收劑具有一光吸收光譜及能夠接收電子，以形成具有不同光吸收光譜的還原電子接收劑，以及其中該氧化分子感光劑與該還原電子接收劑之間電荷分離係維持在持續照射可見光。 2 5 ·如申請專利範圍第2 4項所述之光學資料記錄媒介，其中上述之電子接收劑係由下列分子式之一表示： L，丄， L1 (請先閱讀背面之注意事項再填寫本頁) L·- 經濟部智慧財產局員工消費合作社印製其中 A為说啶結合對位之取代基係部分選自下列群組包含·· -COOH、-B(0H)2、-Ρ03Η2 及-R-p〇3H2，其中 R 為碳氫連結基； B為橋接配合基， L，，可相同或不同，其係選自下列群組之一配合基包含·· NC-(CH2)2-CN、NC-(CH2)3-CN、NC-(CH2)4-CN、鹵素基、 NCS.、草酸基、CO、CN.、NO、吡啶、4-氰吡啶、二苯甲腈、H20、〇H-、NH3、對二氮己環、N〇2-、被一個或更多個甲基取代或未取代的2，2 ’ -二毗啶基及被一個或更多個甲基取代與未取代的1，1〇-二氮雜菲；及 M’，可相同或不同，其係一過渡金屬能夠進行氧化態可逆的變化。第61頁本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） IAW--------^-------- ΛΙΦΜ----------- 526488 A8 B8 C8 D8 六、申請專利範圍一...26·如申請專利範圍第24項所述之光學資料記錄媒介，額外地包含一薄的透明聚合物的薄膜，其中該薄膜位於該記錄層之上。 n n n 1 ϋ n n n n n n n · n n n n n n n 一-0, fl n 1 flail «1« n n ϋ I n * ♦ (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製第62頁本紙張尺度適用中國國家標準（CNS)A4規格（210夂297公釐）(Please read the notes on the back before filling this page) # Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where A is the substituent of the pyridine binding parasite selected from the following groups: -COOH, -B (0H) 2, -P03Η2 and -R-P03H2, wherein R is a carbon-nitrogen linking group; B is a bridging complex;-L ', which may be the same or different, is selected from one of the following groups. The complex includes: NC -(CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halo, NCS, oxalate, CO, CN., NO, pyridine, 4-cyanopyridine , Dibenzoyl, H20, OH ·, NH3, p-diazepine, N02 ·, 2,2'-dipyridinyl substituted or unsubstituted by one or more methyl groups and by one or more Each methyl substituted and unsubstituted MO-diazaphenanthrene; and M ′, which may be the same or different, is a transition metal capable of undergoing oxidation states. Page 55 ^ J · ϋ II tm— n ϋ n I nn I nnn ϋ nn nnnnn 1 · I ϋ I n ϋ ϋ «I n I This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 526488 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B 8 C8 D8 6. Scope of patent application Reversible changes. 17 · The binary data recording medium as described in item 11 of the declared patent scope, which additionally comprises a thin transparent polymer film, wherein the film is located on the green layer. 18. A method for storing data in an optically readable form, comprising: (I) providing a photochromic metal complex on a substrate, the photochromic complex absorbing a first wavelength of visible light; ( II) Immerse the substrate and the attached photochromic complex in a liquid containing a complex compound; (iu) irradiate the photochromic metal complex attached to the substrate in a selected range to initiate a photoreaction The resulting reaction between the metal complex and the coordination compound produces a reaction product on the substrate, which absorbs light of a second wavelength, and the first and second wavelengths are selected to correspond to binary data storage Code; and (iv) remove excess coordination compounds to make the reaction irreversible. 1 9. A method for recovering data stored in an optically readable form, comprising: (i) providing an optical data storage medium comprising a metal complex on a substrate, wherein the metal complex is The original state and a reaction state exist. The original state has an absorption or emission spectrum different from that of the reaction state. The range of the metal complex in the original state corresponds to a binary value. National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the notes on the back before filling out this page) Φ Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 526488 A8 B8 I-C8 ------ -D8 ____ VI. Patent application scope Erpo long visible light; and (Π) irradiate the non-oxidized molecular photosensitizer in the selected range to cause an electron to enter the empty conductive belt of the substrate, and then the electron receiver Receives the electron, thereby forming an oxidized molecular photosensitizer that absorbs light of a third wavelength, thereby forming a reduced electron receiving agent that absorbs the first Wavelength of light, the wavelength of the third and fourth compositions is selected to correspond to the binary codes stored data. 22 · A method for recovering data stored in an optically readable form, comprising: (1) providing an optical data storage medium including a molecular photosensitizer and an electron acceptor adsorbed on a semiconductor substrate with a wide energy gap Wherein one or more regions of the medium are oxidized molecular sensitizers or reduced electron acceptors, wherein the oxidized molecular sensitizers have an absorption or emission spectrum different from that of molecular sensitizers in an unoxidized form, wherein The reduced electron-receiving agent has an absorption or emission spectrum different from that of the unreduced electron-receiving agent. The range of the oxidized molecular photosensitizer and the range of the reduced electron-receiving agent correspond to binary values. The range of the molecular sensitizer's unoxidized state corresponds to the range of the reduced electron receiver's non-reduced state; the molecular sensitizer is represented by one of the following molecular formulas: [M (NN) 2L2] n [M (NN) L4] n [M (NNN) L3] n page 58 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------------- ------- ^ --- ------ ^ — ^ 1. Meal * (Please read the notes on the back before filling out this page) A8 B8 C8 D8 526488 6. Scope of patent application and [M (NNN) 2] n where M is a transition The metal has an oxidation state; the poly-p-pyridine complex having N-N as a chromophore has a charge and binds to one or two substituents selected from the group consisting of: -COOH, -B (〇η) 2, _ ΡΟ3Η2 and -RP〇sH2, where R is a saturated or an aromatic carbon 4 gas group; the tripyridyl complex of NNN is a chromophore having an electric charge and binding selected from one to three substituents of the group consisting of:- COOH, -B (〇H) 2, -PChH2, -R-POsH2, and phenyl, wherein the phenyl group is combined with one or more substituents selected from the group consisting of: -COOH, -B (OH) 2 -P〇3h2 and -R-P03H2, where R is a saturated or an aromatic hydrocarbon group; L is a non-chromophore monodentate or polydentate accessory ligand having a charge; and η is a total charge number including M oxidation Algebraic sum of states and ligand charges; (ii) reflecting a light beam deviating from the medium, wherein the light beam has a wavelength selectively separated by the oxidized molecular photosensitizer or the unoxidized state Absorption by one of the photosensitizers; and (iii) detecting the intensity of the light beam after the light beam is reflected by the medium, wherein the reflected light beam intensity indicates that the light beam penetrates the range of the oxidized molecular photosensitizer and the reduced electron receiving agent or The range of the molecular sensitizer in the unoxidized state and the electron receiver in the reduced state, and thus the binary value stored in the recording medium is restored. Page 59 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --------------------- Order ------ --- According to Han > (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives 526488 A8 B8 C8 D8 VI. Patented oxidized molecular photosensitizers with different light absorption spectra Wherein the electron-receiving agent has a light absorption spectrum and is capable of receiving electrons to form reduced electron-receiving agents having different light absorption spectra, and wherein the charge separation system between the oxidized molecular photosensitizer and the reduced electron-receiving agent is maintained continuously Visible light. 2 5 · The optical data recording medium as described in item 24 of the scope of patent application, wherein the above electron-receiving agent is represented by one of the following molecular formulas: L, 丄, L1 (Please read the precautions on the back before filling this page ) L ·-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where A is a substituent group which is said to be a pyridine-binding parasite selected from the group consisting of -COOH, -B (0H) 2, -P03Η2, and -Rp 〇3H2, where R is a hydrocarbon linking group; B is a bridging complex, and L, may be the same or different, which is selected from one of the following groups. The complex includes: NC- (CH2) 2-CN, NC- (CH2) 3-CN, NC- (CH2) 4-CN, halo, NCS., Oxalate, CO, CN., NO, pyridine, 4-cyanopyridine, dibenzonitrile, H20, OH-, NH3, p-diazepine, No. 2-, 2,2'-dipyridyl substituted or unsubstituted with one or more methyl groups, and unsubstituted 1 with one or more methyl groups , 10-diazaphenanthrene; and M ', which may be the same or different, which is a transition metal capable of reversibly changing the oxidation state. Page 61 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) IAW -------- ^ -------- ΛΙΦΜ --------- -526488 A8 B8 C8 D8 VI. Patent application scope I ... 26. The optical data recording medium described in item 24 of the patent application scope additionally includes a thin transparent polymer film, where the film is located in the Above the recording layer. nnn 1 ϋ nnnnnnn · nnnnnnn a -0, fl n 1 flail «1« nn ϋ I n * ♦ (Please read the notes on the back before filling out this page) Printed on page 62 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Paper size applies to China National Standard (CNS) A4 (210 夂 297 mm)