JP2006178399A - Two-photon absorption material comprising of porphyrin arrays - Google Patents
Two-photon absorption material comprising of porphyrin arrays Download PDFInfo
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- JP2006178399A JP2006178399A JP2005227989A JP2005227989A JP2006178399A JP 2006178399 A JP2006178399 A JP 2006178399A JP 2005227989 A JP2005227989 A JP 2005227989A JP 2005227989 A JP2005227989 A JP 2005227989A JP 2006178399 A JP2006178399 A JP 2006178399A
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- porphyrin
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 125000006253 t-butylcarbonyl group Chemical group [H]C([H])([H])C(C(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
この発明は、2光子吸収材料、及びこれに用いられるポルフィリン系化合物に関する。 The present invention relates to a two-photon absorption material and a porphyrin-based compound used therefor.
近年、有機化合物の有する非線形光学特性の中でも、特に多光子吸収現象が注目されている。 In recent years, among the nonlinear optical characteristics of organic compounds, the multiphoton absorption phenomenon has attracted attention.
多光子吸収とは、化合物が数個の光子を吸収して基底状態から励起状態へ遷移する現象である。特に2光子吸収現象においては、1光子励起波長の2倍程度の波長の光を用いて、2個の光子を1つの分子に当てることにより励起させることができる。1個の分子に同時に2個の光子が当たる確率は、光子密度の2乗に比例し、試料上でレーザー光が焦点を結ぶとき焦点面から離れるにつれ、光子密度は距離の2乗に比例して減少する。従って、2光子吸収の起こる確率は焦点面から離れるに伴い距離の4乗に比例して減少していく。この現象を利用して、光メモリ、2光子造形、2光子フォトダイナミックセラピー等の分野で2光子吸収の応用が期待されている。 Multiphoton absorption is a phenomenon in which a compound absorbs several photons and transitions from a ground state to an excited state. In particular, in the two-photon absorption phenomenon, excitation can be performed by applying two photons to one molecule using light having a wavelength about twice the one-photon excitation wavelength. The probability that two photons hit one molecule at a time is proportional to the square of the photon density, and as the laser beam is focused on the sample, the photon density is proportional to the square of the distance as it moves away from the focal plane. Decrease. Accordingly, the probability that two-photon absorption occurs decreases as the distance from the focal plane increases in proportion to the fourth power of the distance. Utilizing this phenomenon, application of two-photon absorption is expected in the fields of optical memory, two-photon modeling, two-photon photodynamic therapy, and the like.
また、2光子吸収した励起状態から輻射失活過程において発光する2光子発光は、入射した光の波長より短波長の光(=エネルギーの高い光)を取り出せるため、光変換材料、光増感剤としても研究がなされている。この2光子吸収特性を有する化合物として、下記の式(A−1)にかかる化合物や、非特許文献1に記載されたポルフィリン類誘導体等が知られている。 In addition, two-photon emission that emits light in a radiation deactivation process from an excited state that has been absorbed by two photons can extract light having a wavelength shorter than the wavelength of the incident light (= light with high energy). As well as research. Known compounds having the two-photon absorption property include compounds according to the following formula (A-1), porphyrin derivatives described in Non-Patent Document 1, and the like.
ところで、2光子吸収特性の指標として2光子吸収断面積があり、この値が高いほど一般的に2光子吸収特性は良好であると言える。一般的に、2光子吸収断面積の大きい化合物として現在期待されているものの1つがポルフィリン系化合物である。特許文献1には2,000GM程度の2光子吸収断面積を有するポルフィリン誘導体を用いた2光子吸収材料の記載があるが、この値は光メモリなどへの応用には不十分である。また、非特許文献1には、縮環ポルフィリン2量体を用いた2光子吸収材料が記載されており、たとえば下記化合物(A−2)は測定波長800nmで14,000GMもの高い2光子吸収断面積を有する旨が記載されている。しかし、この化合物は特許文献1における2光子吸収測定波長域である800nmを含め幅広い波長領域に実吸収を有しており、2光子吸収断面積測定時における1光子吸収効果を除去できていない。そのため、実際の2光子吸収断面積は見かけ上のそれよりも低いことが予想される。また、記録媒体として用いた場合、1光子吸収が存在することは、熱効果による記録信号の乱れが生じやすい点でも不利である。さらに、下記化合物(A−2)はその著しい平面性の高さゆえ、溶剤への溶解性及び媒体塗布時の膜性に大きく劣ることが容易に予想され、光メモリ用途としては不適であると考えられていた。以上の理由から、大きな二光子吸収断面積を有し、かつ長波長領域に吸収を有さない2光子吸収材料の開発が望まれてきた。 By the way, there is a two-photon absorption cross section as an index of the two-photon absorption characteristics, and it can be said that the higher the value, the better the two-photon absorption characteristics. In general, one of the compounds currently expected as a compound having a large two-photon absorption cross section is a porphyrin-based compound. Patent Document 1 describes a two-photon absorption material using a porphyrin derivative having a two-photon absorption cross section of about 2,000 GM, but this value is insufficient for application to an optical memory or the like. Non-Patent Document 1 describes a two-photon absorption material using a condensed ring porphyrin dimer. For example, the following compound (A-2) has a two-photon absorption cutoff as high as 14,000 GM at a measurement wavelength of 800 nm. The fact that it has an area is described. However, this compound has actual absorption in a wide wavelength region including 800 nm which is the two-photon absorption measurement wavelength region in Patent Document 1, and the one-photon absorption effect at the time of measuring the two-photon absorption cross section cannot be removed. Therefore, the actual two-photon absorption cross section is expected to be lower than the apparent one. Further, when used as a recording medium, the presence of one-photon absorption is disadvantageous in that the recording signal is easily disturbed by a thermal effect. Furthermore, the following compound (A-2) is expected to be greatly inferior in solubility in a solvent and film property at the time of coating a medium because of its remarkably high flatness, and is considered unsuitable for optical memory applications. It was done. For the above reasons, it has been desired to develop a two-photon absorption material having a large two-photon absorption cross section and having no absorption in a long wavelength region.
そこで、この発明は、上記従来の実情に鑑みてなされたものであって、高い2光子吸収断面積を有しながら、700nmを超える長波長域には実吸収を有しない化合物を用いた2光子吸収材料を提供することを目的とする。 Thus, the present invention has been made in view of the above-described conventional situation, and has two photons using a compound having a high two-photon absorption cross-section and having no actual absorption in a long wavelength region exceeding 700 nm. An object is to provide an absorbent material.
本発明者らは鋭意検討した結果、ポルフィリン骨格同士が最低2箇所、直接又は他のユニットを介して結合することよりなる多量体であって、この多量体分子中において、隣接する各ポルフィリン平面同士の二面角が平均して10〜80度に制御されていることを特徴とするポルフィリン多量体を部分構造として含む化合物を用いた2光子吸収材料、好ましくは下記の式(1)で示すポルフィリン多量体を部分構造として含む化合物を用いた2光子吸収材料が好適な2光子吸収特性を示すことを見出し、本発明を完成させたものである。 As a result of intensive studies, the present inventors have found that the porphyrin skeletons are multimers formed by bonding at least two positions directly or via other units, and in the multimer molecule, adjacent porphyrin planes are adjacent to each other. Is a two-photon absorption material using a compound containing a porphyrin multimer as a partial structure, preferably a porphyrin represented by the following formula (1): The inventors have found that a two-photon absorption material using a compound containing a multimer as a partial structure exhibits suitable two-photon absorption characteristics, and completed the present invention.
また、上記式(1)において、各リンカーL1〜Ln+1と、ポルフィリン環A,B1〜Bn,Cとの結合の種類がそれぞれ共有結合、配位結合、水素結合のいずれかより成るポルフィリン多量体を構造中に含む化合物を用いた2光子吸収材料を用いることができる。 In the above formula (1), the types of bonds between the linkers L 1 to L n + 1 and the porphyrin rings A, B 1 to B n , and C are any of covalent bonds, coordinate bonds, and hydrogen bonds, respectively. A two-photon absorption material using a compound containing a porphyrin multimer in the structure can be used.
さらに、ポルフィリン環A及びCが、それぞれ独立に下記式(2)で示されるポルフィリン環であり、ポルフィリン環B1〜Bnがそれぞれ独立に式(3)で示されるポルフィリン環であるポルフィリン多量体を構造中に含む化合物を用いた2光子吸収材料を用いることができる。 Further, porphyrin rings A and C are each independently a porphyrin ring represented by the following formula (2), and porphyrin rings B 1 to B n are each independently a porphyrin ring represented by the formula (3). A two-photon absorption material using a compound containing in the structure can be used.
さらにまた、下記式(1)で表されるポルフィリン多量体を構造中に含むポルフィリン系化合物やこのポルフィリン系化合物を用いた2光子吸収材料を用いることができる。 Furthermore, a porphyrin-based compound containing a porphyrin multimer represented by the following formula (1) in the structure or a two-photon absorption material using the porphyrin-based compound can be used.
また、上記の式(2),(3)において、R4〜R19が、それぞれ独立に水素原子、置換基を有していても良い炭素数1〜20のアルキル基、及びハロゲンのいずれかであり、R3が水素原子であり、式(4)において、R46が炭素数1〜20の置換基を有していても良いアルキル基であり、かつR47及びR48がそれぞれ独立に水素原子もしくは炭素数1〜20の置換基を有していてもよいアルキル基であるポルフィリン系化合物やこのポルフィリン系化合物を用いた2光子吸収材料を用いることができる。 In the above formulas (2) and (3), R 4 to R 19 are each independently any one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a halogen. R 3 is a hydrogen atom, and in Formula (4), R 46 is an alkyl group which may have a substituent having 1 to 20 carbon atoms, and R 47 and R 48 are each independently A porphyrin compound which is a hydrogen atom or an alkyl group which may have a substituent having 1 to 20 carbon atoms, or a two-photon absorption material using the porphyrin compound can be used.
さらに、リンカーL1〜Ln+1が、各々独立に式(5)に記載の化合物であり、このリンカーが各ポルフィリン環に水素結合を介して結合するポルフィリン多量体を構造中に含む化合物を用いた2光子吸収材料を用いることができる。 Furthermore, each of the linkers L 1 to L n + 1 is independently a compound described in the formula (5), and a compound containing a porphyrin multimer in which this linker is bonded to each porphyrin ring via a hydrogen bond is used. A two-photon absorbing material can be used.
さらにまた、リンカーL1〜Ln+1が、各々独立に式(6)記載の構造を有し、このリンカーとポルフィリン環A,B1〜Bn,Cとが共有結合によりに結合されているポルフィリン多量体を構造中に含む化合物を用いた2光子吸収材料を用いることができる。 Furthermore, each of the linkers L 1 to L n + 1 independently has the structure described in the formula (6), and the porphyrin in which the linker and the porphyrin rings A, B 1 to B n and C are bonded by a covalent bond. A two-photon absorption material using a compound containing a multimer in the structure can be used.
この発明に記載の環状ポルフィリン化合物は、高い2光子吸収断面積を示し、700nm以上の長波長域に吸収を有さないことから、該化合物を含む高性能な2光子吸収材料を提供できることが期待される。 The cyclic porphyrin compound described in the present invention exhibits a high two-photon absorption cross-section and does not have absorption in a long wavelength region of 700 nm or more, and thus is expected to provide a high-performance two-photon absorption material containing the compound. Is done.
以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものでなく、その要旨の範囲内で種々に変更して実施することができる。 Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
この発明にかかる2光子吸収材料とは、ポルフィリン骨格同士が最低2箇所、直接又は他のユニットを介して結合することよりなる多量体であって、この多量体分子中において、隣接する各ポルフィリン平面の二面角が平均して10〜80度に制御されていることを特徴とするポルフィリン多量体を部分構造として含む化合物を用いた2光子吸収材料、好ましくは式(1)で示すポルフィリン多量体を部分構造として含む化合物を用いた2光子吸収材料である。 The two-photon absorption material according to the present invention is a multimer formed by bonding porphyrin skeletons to each other at least two places, directly or via other units, and each adjacent porphyrin plane in the multimer molecule. The two-photon absorption material using a compound containing a porphyrin multimer as a partial structure, preferably a porphyrin multimer represented by the formula (1), characterized in that the dihedral angle is controlled to 10 to 80 degrees on average Is a two-photon absorption material using a compound containing as a partial structure.
なお、本発明において、芳香環とは、芳香族性を有する環、すなわち(4m+2)π電子系(mは自然数)を有する環を意味する。その骨格構造は、通常、5又は6員環の、単環又は2〜6縮合環からなる芳香環であり、この芳香環には、芳香族炭化水素環、芳香族複素環の他、アントラセン環、カルバゾール環、アズレン環のような縮合環も含まれる。 In the present invention, the aromatic ring means a ring having aromaticity, that is, a ring having a (4m + 2) π electron system (m is a natural number). The skeleton structure is usually an aromatic ring consisting of a 5- or 6-membered monocyclic ring or a 2-6 condensed ring. This aromatic ring includes an aromatic hydrocarbon ring, an aromatic heterocyclic ring, and an anthracene ring. , Condensed rings such as a carbazole ring and an azulene ring are also included.
また、本発明において、「芳香環基」等の「…環基」とは、芳香環等の環から水素原子を1個とった、1価の置換基をいう。さらに、「非芳香環置換基」とは、置換基を有してもよい芳香環でない全ての置換基をいい、アミノ基やハロゲン等の炭素数0の置換基も含む。また、「置換基を有していても良い」とは、置換基を1以上有していても良いことを意味する。 In the present invention, “... ring group” such as “aromatic ring group” means a monovalent substituent having one hydrogen atom from a ring such as an aromatic ring. Furthermore, the “non-aromatic ring substituent” refers to all substituents that may have a substituent and which is not an aromatic ring, and includes substituents having 0 carbon atoms such as amino groups and halogens. Further, “may have a substituent” means that it may have one or more substituents.
[A〜C]
<A〜Cの構造>
上記の式(1)中、A、B1〜Bn、及びCは、各々独立にポルフィリン環を表し、A及びCは特に好ましくは、式(2)で示されるポルフィリン環であり、B1〜Bnは特に好ましくは、式(3)で示されるポルフィリン環である。
[A to C]
<Structure of A to C>
In the above formula (1), A, B 1 to B n and C each independently represent a porphyrin ring, and A and C are particularly preferably a porphyrin ring represented by the formula (2), and B 1 ~ Bn is particularly preferably a porphyrin ring represented by the formula (3).
これらのうち、Ar1〜Ar4は、それぞれ独立に置換基を有していてもよい芳香環を表す。さらに、それぞれのポルフィリン骨格は、a、b及びcの位置でそれぞれ他のポルフィリン骨格に結合する。 Among these, Ar < 1 > -Ar < 4 > represents the aromatic ring which may have a substituent each independently. Further, each porphyrin skeleton is bonded to another porphyrin skeleton at positions a, b and c.
<Ar1〜Ar4の骨格構造>
Ar1〜Ar4の骨格構造の具体例としては、5員環単環としてフラン環、チオフェン環、ピロール環、イミダゾール環、チアゾール環、オキサジアゾール環、6員環単環としてベンゼン環、ピリジン環、ピラジン環、縮合環としてナフタレン環、フェナンスレン環、アズレン環、ピレン環、キノリン環、イソキノリン環、キノキサリン環、ベンゾフラン環、カルバゾール環、ジベンゾチオフェン環、アントラセン環等があげられる。これらのうち、合成上の理由から単環が好ましく、さらに好ましくは6員環の単環であり、特に好ましくはベンゼン環である。
<Ask structure of Ar 1 to Ar 4 >
Specific examples of the skeleton structure of Ar 1 to Ar 4 include a furan ring, a thiophene ring, a pyrrole ring, an imidazole ring, a thiazole ring, an oxadiazole ring as a 5-membered monocyclic ring, a benzene ring as a 6-membered monocyclic ring, and pyridine. Examples of the ring, pyrazine ring and condensed ring include naphthalene ring, phenanthrene ring, azulene ring, pyrene ring, quinoline ring, isoquinoline ring, quinoxaline ring, benzofuran ring, carbazole ring, dibenzothiophene ring, anthracene ring and the like. Of these, a monocyclic ring is preferred for reasons of synthesis, a 6-membered monocyclic ring is more preferred, and a benzene ring is particularly preferred.
なお、Ar1〜Ar4はそれぞれ異なる方が溶解性及び記録層形成時の膜性向上の点で好ましいが、同じである方が合成上の点から好ましい。 Ar 1 to Ar 4 are preferably different from the viewpoint of solubility and improvement in film properties when forming the recording layer, but the same is preferable from the viewpoint of synthesis.
<Ar1〜Ar4が有する置換基>
Ar1〜Ar4はそれぞれ置換基を有していても良い。Ar1〜Ar4が有する置換基としては、炭素数1〜20のアルキル基、アルケニル基、アルキニル基、炭化水素環基、複素環基、アルコキシ基、アルキルカルボニル基、(ヘテロ)アリールオキシ基、(ヘテロ)アラルキルオキシ基等があげられ、更に置換基を有していても良いアミノ基、ニトロ基、シアノ基、エステル基、ハロゲン原子、水酸基などがあげられる。
<Substituents Ar 1 to Ar 4 have>
Ar 1 to Ar 4 may each have a substituent. Examples of the substituent that Ar 1 to Ar 4 have include an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, a hydrocarbon ring group, a heterocyclic group, an alkoxy group, an alkylcarbonyl group, a (hetero) aryloxy group, Examples thereof include (hetero) aralkyloxy groups, and further examples include an optionally substituted amino group, nitro group, cyano group, ester group, halogen atom, and hydroxyl group.
さらに、好ましくは、炭素数1〜20のアルキル基、炭素数2〜20のアルケニル基、炭素数2〜20のアルキニル基、炭素数3〜20の炭化水素環基、5又は6員環の単環又は2〜6縮合環由来の複素環基、炭素数1〜9のアルコキシ基、炭素数2〜18のアルキルカルボニル基、炭素数2〜18の(ヘテロ)アリールオキシ基、炭素数3〜18の(ヘテロ)アラルキルオキシ基、アミノ基、炭素数2〜20のアルキルアミノ基、炭素数2〜30の(ヘテロ)アリールアミノ基、ニトロ基、シアノ基、炭素数2〜6のエステル基、ハロゲン原子、水酸基などがあげられる。 Further, preferably, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a hydrocarbon ring group having 3 to 20 carbon atoms, a single unit of a 5- or 6-membered ring. A heterocyclic group derived from a ring or a 2-6 condensed ring, an alkoxy group having 1 to 9 carbon atoms, an alkylcarbonyl group having 2 to 18 carbon atoms, a (hetero) aryloxy group having 2 to 18 carbon atoms, or 3 to 18 carbon atoms (Hetero) aralkyloxy group, amino group, alkylamino group having 2 to 20 carbon atoms, (hetero) arylamino group having 2 to 30 carbon atoms, nitro group, cyano group, ester group having 2 to 6 carbon atoms, halogen An atom, a hydroxyl group, etc. are mention | raise | lifted.
上記の炭素数1〜20のアルキル基の例としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、iso−ブチル基、sec−ブチル基、tert−ブチル基、ヘキシル基、オクチル基などがあげられる。
上記の炭素数2〜20のアルケニル基の例としては、ビニル基、プロペニル基、ブテニル基、2−メチル−1−プロペニル基、ヘキセニル基、オクテニル基などがあげられる。
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, hexyl group, and octyl group. Etc.
Examples of the alkenyl group having 2 to 20 carbon atoms include a vinyl group, a propenyl group, a butenyl group, a 2-methyl-1-propenyl group, a hexenyl group, and an octenyl group.
上記の炭素数2〜20のアルキニル基の例としては、エチニル基、プロピニル基、ブチニル基、2−メチル−1−プロピニル基、ヘキシニル基、オクチニル基などがあげられる。
上記の炭素数3〜20の炭化水素環基の例としてはシクロプロピル基、シクロヘキシル基、シクロヘキセニル基、テトラデカヒドロアントラニル基、フェニル基、アントラニル基、フェナンスリル基、フェロセニル基などがあげられる。
Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group, octynyl group and the like.
Examples of the hydrocarbon ring group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclohexyl group, a cyclohexenyl group, a tetradecahydroanthranyl group, a phenyl group, an anthranyl group, a phenanthryl group, and a ferrocenyl group.
上記の5又は6員環の単環又は2〜6縮合環由来の複素環基の例としては、ピリジル基、チエニル基、ベンゾチエニル基、カルバゾリル基、キノリニル基、2−ピペリジニル基、2−ピペラジニル基、オクタヒドロキノリニル基などがあげられる。
上記の炭素数1〜9のアルコキシ基の例としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、iso−ブトキシ基、sec−ブトキシ基、tert−ブトキシ基、ヘキシルオキシ基、オクチルオキシ基などがあげられる。
Examples of the 5- or 6-membered monocyclic or heterocyclic groups derived from 2 to 6 condensed rings include pyridyl, thienyl, benzothienyl, carbazolyl, quinolinyl, 2-piperidinyl, 2-piperazinyl Group, octahydroquinolinyl group and the like.
Examples of the alkoxy group having 1 to 9 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, hexyloxy group, And octyloxy group.
上記の炭素数2〜18のアルキルカルボニル基の例としては、メチルカルボニル基、エチルカルボニル基、イソプロピルカルボニル基、tert−ブチルカルボニル基、シクロヘキシルカルボニル基などがあげられる。
上記の炭素数2〜18の(ヘテロ)アリールオキシ基の例としては、フェノキシ基、ナフチルオキシ基等のアリールオキシ基や、2−チエニルオキシ基、2−フリルオキシ基、2−キノリルオキシ基等のヘテロアリールオキシ基などがあげられる。
Examples of the alkylcarbonyl group having 2 to 18 carbon atoms include a methylcarbonyl group, an ethylcarbonyl group, an isopropylcarbonyl group, a tert-butylcarbonyl group, a cyclohexylcarbonyl group, and the like.
Examples of the (hetero) aryloxy group having 2 to 18 carbon atoms include aryloxy groups such as phenoxy group and naphthyloxy group, 2-thienyloxy group, 2-furyloxy group, and 2-quinolyloxy group. And heteroaryloxy group.
上記の炭素数3〜18の(ヘテロ)アラルキルオキシ基の例としては、ベンジルオキシ基、フェネチルオキシ基、ナフチルメトキシ基等のアラルキルオキシ基や、2−チエニルメトキシ基、2−フリルメトキシ基、2−キノリルメトキシ基等のヘテロアラルキルオキシ基などがあげられる。
上記の炭素数2〜20のアルキルアミノ基の例としては、エチルアミノ基、ジメチルアミノ基、メチルエチルアミノ基、ジブチルアミノ基、ピペリジル基などがあげられる。
Examples of the (hetero) aralkyloxy group having 3 to 18 carbon atoms include aralkyloxy groups such as benzyloxy group, phenethyloxy group and naphthylmethoxy group, 2-thienylmethoxy group, 2-furylmethoxy group, 2 -Heteroaralkyloxy group such as quinolylmethoxy group.
Examples of the alkylamino group having 2 to 20 carbon atoms include an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, and a piperidyl group.
上記の炭素数2〜30の(ヘテロ)アリールアミノ基の例としては、ジフェニルアミノ基、ジナフチルアミノ基、ナフチルフェニルアミノ基、ジトリルアミノ基等のアリールアミノ基や、ジ(2−チエニル)アミノ基、ジ(2−フリル)アミノ基、フェニル(2−チエニル)アミノ基等のヘテロアリールアミノ基などがあげられる。
上記の炭素数2〜6のエステル基の例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、tert−ブトキシカルボニル基などがあげられる。
上記のハロゲン原子の例としては、フッ素原子、塩素原子、臭素原子、沃素原子などがあげられる。
Examples of the (hetero) arylamino group having 2 to 30 carbon atoms include arylamino groups such as diphenylamino group, dinaphthylamino group, naphthylphenylamino group, and ditolylamino group, and di (2-thienyl) amino group. And heteroarylamino groups such as a di (2-furyl) amino group and a phenyl (2-thienyl) amino group.
Examples of the ester group having 2 to 6 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, tert-butoxycarbonyl group and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Ar1〜Ar4がそれぞれ置換基を有する場合、この置換基同士が結合して環状構造をなしてもよい。例えば、Ar1〜Ar4がベンゼン環由来の基である場合、このベンゼン環が有する置換基同士が結合して環状構造を形成している例として、下記式(7)に示すような3種類の構造を例としてあげることができる。なお、下記式(7)において、eの部分がポルフィリン環への結合位置である。 When Ar 1 to Ar 4 each have a substituent, the substituents may be bonded to each other to form a cyclic structure. For example, when Ar 1 to Ar 4 are groups derived from a benzene ring, three examples as shown in the following formula (7) are examples in which substituents of the benzene ring are bonded to form a cyclic structure. The structure can be given as an example. In the following formula (7), the part e is the bonding position to the porphyrin ring.
なお、Ar1〜Ar4は置換基を有することが化合物の溶解性向上の面で好ましい。 Ar 1 to Ar 4 preferably have a substituent in terms of improving the solubility of the compound.
[R3]
R3は水素原子もしく炭素数0〜20の非芳香環置換基もしくは置換基を有していても良い芳香環を表す。炭素数0〜20の非芳香環置換基の具体例としては、上記Ar1〜Ar4が有していても良い置換基としてあげられた非芳香環置換基の具体例が相当し、置換基を有していても良い芳香環の具体例としては上記Ar1〜Ar4の具体例が相当する。
なお、R3は芳香環であることが化合物の安定性向上の面で好ましいが、合成面からは水素原子であることが好ましい。
[R 3 ]
R 3 represents a hydrogen atom or a non-aromatic ring substituent having 0 to 20 carbon atoms or an aromatic ring which may have a substituent. Specific examples of the non-aromatic ring substituent having 0 to 20 carbon atoms correspond to the specific examples of the non-aromatic ring substituent listed as the substituents that Ar 1 to Ar 4 may have. As specific examples of the aromatic ring which may have, the above specific examples of Ar 1 to Ar 4 are equivalent.
R 3 is preferably an aromatic ring from the viewpoint of improving the stability of the compound, but from the viewpoint of synthesis, it is preferably a hydrogen atom.
[R4〜R19]
R4〜R19はそれぞれ独立に水素原子もしくは炭素数0〜20の置換基を表す。その具体例としては、上記Ar1〜Ar4が有していても良い置換基としてあげられた具体例が相当する。なお、これらのうち、合成上の理由からR4〜R19はそれぞれ水素原子もしくはハロゲン原子であることが好ましく、R1〜R8がそれぞれハロゲン原子であることがポルフィリン系化合物の安定性向上の面で特に好ましいが、合成面からはR4〜R19はそれぞれ水素原子であることが特に好ましい。
[R 4 to R 19 ]
R 4 to R 19 each independently represents a hydrogen atom or a substituent having 0 to 20 carbon atoms. Specific examples thereof include specific examples given as the substituents that Ar 1 to Ar 4 may have. Of these, R 4 to R 19 are each preferably a hydrogen atom or a halogen atom for the reasons of synthesis, and R 1 to R 8 are each a halogen atom to improve the stability of the porphyrin-based compound. From the viewpoint of synthesis, R 4 to R 19 are particularly preferably hydrogen atoms.
[M1及びM2]
M1及びM2は、それぞれ独立に2個の水素原子もしくは2価以上の金属イオンを表す。金属元素はポルフィリン環内部に配位し得るものであれば何でもよく、例えばMg,Al,Si,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn,Mo,Ru,Rh,Pd,Ag,Pt,Au,Er等があげられる。
[M 1 and M 2 ]
M 1 and M 2 each independently represent two hydrogen atoms or a divalent or higher valent metal ion. The metal element may be anything as long as it can coordinate inside the porphyrin ring. For example, Mg, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd , Ag, Pt, Au, Er and the like.
これらのうち、化合物の構造及び化学的安定性、吸収波長のチューニングの面からM1及びM2は2価以上の金属イオンであることが好ましく、平面配位をとる金属イオンがさらに好ましく、Co、Ni、Cu、Znが特に好ましい。 Among these, M 1 and M 2 are preferably divalent or higher metal ions from the viewpoint of the structure and chemical stability of the compound and the tuning of the absorption wavelength, more preferably metal ions having a planar coordination, and Co Ni, Cu and Zn are particularly preferable.
[L1〜Ln+1]
上記一般式(1)のL1〜Ln+1はそれぞれ独立にリンカーを表し、特に好ましくは各ポルフィリン環A,B1〜Bn,Cと共有結合、配位結合、水素結合のいずれかを介して結合している。結合の種類の具体例としては、共有結合として、エーテル結合、アミド結合、エステル結合、炭素−炭素二重結合、炭素−窒素二重結合等が、配位結合として、金属−窒素結合、金属−酸素結合などが、水素結合として、水素−酸素結合、水素−窒素結合などがあげられる。
[L 1 to L n + 1 ]
In the above general formula (1), L 1 to L n + 1 each independently represent a linker, and particularly preferably, each porphyrin ring A, B 1 to B n , C is bonded to any one of a covalent bond, a coordinate bond, and a hydrogen bond. Are combined. Specific examples of the type of bond include an ether bond, an amide bond, an ester bond, a carbon-carbon double bond, a carbon-nitrogen double bond, etc. as a covalent bond, and a metal-nitrogen bond, a metal- Examples of hydrogen bonds include hydrogen-oxygen bonds and hydrogen-nitrogen bonds.
これらのうち、リンカーL1〜Ln+1と、ポルフィリン環A,B1〜Bn,Cとの間の結合が共有結合であることが化合物の安定性の面で好ましいが、配位結合もしくは水素結合であることが可逆な分子メモリスイッチを構築できる点で好ましい。なお、L1〜Ln+1の分子量はそれぞれ500以下であることが2光子吸収特性低下防止の面で好ましい。また、リンカーL1〜Ln+1はそれぞれAr1〜Ar4のいずれかに結合していることが合成面及び二面角の制御のしやすさの面で好ましい。 Of these, the bond between the linkers L 1 to L n + 1 and the porphyrin rings A, B 1 to B n and C is preferably a covalent bond in terms of the stability of the compound. Bonding is preferable in that a reversible molecular memory switch can be constructed. The molecular weights of L 1 to L n + 1 are each preferably 500 or less from the viewpoint of preventing deterioration of the two-photon absorption characteristics. The linkers L 1 to L n + 1 are preferably bonded to any one of Ar 1 to Ar 4 in terms of ease of control of the synthesis plane and dihedral angle.
[二面角]
本発明の一般式(1)で表されるポルフィリン多量体において、ポルフィリン環A及びB1間の二面角、Bn及びC間の二面角、A及びC(n=0の場合)間の二面角、n≧2の場合、隣接するBm及びBm+1(mはnより小さい自然数)間の二面角は、それぞれ10〜80度である。これらのうち、2光子吸収断面積向上の面では二面角が大きいことが好ましいが、吸収波長の過度の長波長化防止及び膜性の向上の面では二面角は小さいことが好ましい。なお、ここでポルフィリン環同士の二面角とは、X線結晶構造解析が可能であれば、該解析より見積もられたポルフィン環同士の二面角を表し、X線結晶構造解析が不可能であれば、DFT(B3LYP/6−31G**)法によって計算された最適分子構造におけるポルフィリン環同士の二面角を表す。
[Dihedral angle]
In porphyrin polymer represented by the general formula (1) of the present invention, the dihedral angle between the porphyrin rings A and B 1, the dihedral angle between B n and C, (the case of n = 0) A and C between When n ≧ 2, the dihedral angles between adjacent B m and B m + 1 (m is a natural number smaller than n) are 10 to 80 degrees, respectively. Among these, it is preferable that the dihedral angle is large in terms of improving the two-photon absorption cross-sectional area, but it is preferable that the dihedral angle is small in terms of preventing an excessive increase in the absorption wavelength and improving the film property. Here, the dihedral angle between porphyrin rings represents the dihedral angle between porphin rings estimated from the analysis if X-ray crystal structure analysis is possible, and X-ray crystal structure analysis is impossible. Then, it represents the dihedral angle between porphyrin rings in the optimal molecular structure calculated by the DFT (B3LYP / 6-31G ** ) method.
[n]
nは0〜13の整数を表す。この値が大きいほど2光子吸収特性向上の面で好ましいが、小さい方が化合物の安定性及び合成面で好ましく、特に好ましくはnが0〜2の整数であることである。
[N]
n represents an integer of 0 to 13. A larger value is preferable in terms of improving the two-photon absorption characteristics, but a smaller value is preferable in terms of stability and synthesis of the compound, and particularly preferably n is an integer of 0 to 2.
[本発明に係るポルフィリン系化合物の特に好ましい例1]
本発明に係るポルフィリン系化合物の特に好ましい例としては、Ar1〜Ar4が各々独立に下記一般式(4)で表され、リンカーL1〜Ln+1が各々独立に式(5)で表される構造を有する化合物があげられる。この構造によると、各ポルフィリン環とリンカーとは水素結合を介して結合する。この水素結合構造は、リンカーの種類及び量、温度や圧力、光による刺激等によって、可逆的に水素結合構造を形成及び脱形成しうるため、特に可逆的光メモリ材料を構築する際に有利である。
[Particularly Preferred Example 1 of Porphyrin-Based Compound According to the Present Invention]
As a particularly preferred example of the porphyrin-based compound according to the present invention, Ar 1 to Ar 4 are each independently represented by the following general formula (4), and the linkers L 1 to L n + 1 are each independently represented by the formula (5). And a compound having the following structure. According to this structure, each porphyrin ring and the linker are bonded via a hydrogen bond. This hydrogen bond structure is advantageous particularly when constructing a reversible optical memory material, because it can reversibly form and deform a hydrogen bond structure depending on the type and amount of linker, temperature, pressure, light stimulation, etc. .
式(4)中、R46〜R48はそれぞれ水素原子もしくは炭素数0〜20の置換基を表す。なお、式(4)で表される構造は、式(2)や式(3)で表されるポルフィリン骨格と、dの位置で結合する。また、式(5)は、置換基を有していても良い、環内にY1及びY2を含む環構造を有する化合物を表し、Y1及びY2は、それぞれ第15属原子を表す。 In formula (4), R 46 to R 48 each represent a hydrogen atom or a substituent having 0 to 20 carbon atoms. In addition, the structure represented by Formula (4) couple | bonds with the porphyrin skeleton represented by Formula (2) or Formula (3) in the position of d. Moreover, Formula (5) represents the compound which has a ring structure which may have a substituent and contains Y < 1 > and Y < 2 > in a ring, Y < 1 > and Y < 2 > represent a 15th group atom, respectively. .
[R46〜R48]
これらのうち、R46〜R48の具体例としては上述のAr1〜Ar4が有していても良い置換基としてあげられた具体例が相当する。
[R 46 to R 48 ]
Among these, specific examples of R 46 to R 48 correspond to the specific examples given as the substituents that Ar 1 to Ar 4 may have.
[Y1及びY2]
Y1及びY2は15属原子を表し、その具体例としては、N、P等があげられる。これらのうち、Nであることが合成面で好ましい。
[Y 1 and Y 2 ]
Y 1 and Y 2 represent a Group 15 atom, and specific examples thereof include N and P. Of these, N is preferable in terms of synthesis.
[式(8)で示される環状構造]
式(8)で示される環状構造は、置換基を有していても良い、環内にY1及びY2を含む環構造を表す。環を構成する原子数は5〜7であることが好ましく、Y1、Y2以外の構成原子としてはC、N、Oが好ましく、Cが特に好ましい。その具体例としては、5員環としては例えば以下の式(8)〜(10)記載の構造があげられ、6員環としては例えば以下の式(11)〜(13)記載の構造があげられる。これらのうち、6員環であることが水素結合構造の構築のしやすさの面で好ましい。また、環が有していてもよい置換基としては、上述のAr1〜Ar4が有していても良い置換基としてあげられた具体例が相当する。
[Circular structure represented by formula (8)]
The cyclic structure represented by the formula (8) represents a cyclic structure containing Y 1 and Y 2 in the ring, which may have a substituent. The number of atoms constituting the ring is preferably 5 to 7, and as constituent atoms other than Y 1 and Y 2 , C, N and O are preferable, and C is particularly preferable. As specific examples thereof, examples of the 5-membered ring include the structures described in the following formulas (8) to (10), and examples of the 6-membered ring include the structures described in the following formulas (11) to (13). It is done. Among these, a 6-membered ring is preferable from the viewpoint of easy construction of a hydrogen bond structure. Further, examples of the substituent that the ring may have correspond to the specific examples given as the substituent that Ar 1 to Ar 4 may have.
なお、Y1及びY2の環内における位置については、隣接するポルフィン環の「Ar1とAr3又はAr3同士」あるいは「Ar2とAr4又はAr4同士」が有する、式(4)に示す構造とY1及びY2の2箇所で水素結合できる位置にあることが好ましく、特に好ましくはY1とY2の間に炭素原子を1つ挟むような位置であることである。 Note that the position in Y 1 and Y 2 in the ring, with the "Ar 1 and Ar 3 or Ar 3 each other" or "Ar 2 and Ar 4 or Ar 4 between" adjacent porphine ring, formula (4) preferably in the position capable of hydrogen bonding at two positions of the structures and Y 1 and Y 2 shown in, it is especially preferably positioned as to sandwich one carbon atom between Y 1 and Y 2.
[ポルフィリン環とリンカーの混合比]
上記のポルフィリン多量体とリンカーの混合比については、ポルフィリン多量体を構成するポルフィリン単環1に対して通常リンカー1〜2,000であり、10〜1,000であることが2光子吸収特性向上の面で好ましく、100〜500であることが特に好ましい。
[Mixing ratio of porphyrin ring and linker]
Regarding the mixing ratio of the porphyrin multimer and the linker, the linker is usually 1 to 2,000 with respect to the porphyrin monocycle 1 constituting the porphyrin multimer, and 10 to 1,000 is a two-photon absorption property improvement. It is preferable at this surface, and it is especially preferable that it is 100-500.
[本発明に係るポルフィリン系化合物の特に好ましい例2]
また、本発明に係るポルフィリン系化合物の特に好ましい別の例としては、リンカーL1〜Ln+1が各々独立に式(6)で表される構造を有するものがあげられる。この構造によると、各ポルフィリン環とリンカーとは共有結合を介して結合する。よって、溶媒中、固相中、いずれの場合においてもリンカーが脱離し得ないため、特に固体もしくは薄膜として用いる2光子吸収材料に有利である。
[Particularly Preferred Example 2 of Porphyrin-Based Compound According to the Present Invention]
Another particularly preferable example of the porphyrin-based compound according to the present invention is one in which the linkers L 1 to L n + 1 each independently have a structure represented by the formula (6). According to this structure, each porphyrin ring and the linker are bonded via a covalent bond. Therefore, since the linker cannot be detached in any case, in a solvent or in a solid phase, it is particularly advantageous for a two-photon absorption material used as a solid or a thin film.
[X1及びX2]
X1及びX2は、それぞれ独立にエーテル構造、エステル構造、カルボニル構造、アミノ構造、アミド構造、シッフ塩基構造のいずれかを表す。ここで、本発明におけるエーテル構造とは、−Q1−(Q1は16属原子)で表される構造を表し、エステル構造とは、−(C=Q2)−O−(Q2は16属原子)で表される構造を表し、カルボニル構造とは、−(C=Q3)−(Q3は16属原子)で表される構造を表し、アミノ構造とは、−NR75−(R75は水素原子もしくは炭素数0〜20の置換基)で表される構造を表し、アミド構造とは、−(C=Q4)−NR76−(Q4は16属原子、R76は水素原子もしくは炭素数0〜20の置換基)を表し、シッフ塩基構造とは、−C=N−で表される構造を表す。なお、R75及びR76における炭素数0〜20の置換基の具体例としては上述のAr1〜Ar4が有していても良い置換基としてあげられた具体例が相当する。
[X 1 and X 2 ]
X 1 and X 2 each independently represent any of an ether structure, an ester structure, a carbonyl structure, an amino structure, an amide structure, and a Schiff base structure. Here, the ether structure in the present invention represents a structure represented by -Q 1- (Q 1 is a 16 group atom), and the ester structure is-(C = Q 2 ) -O- (Q 2 is 16 group atoms), a carbonyl structure represents a structure represented by — (C═Q 3 ) — (Q 3 is a 16 group atom), and an amino structure represents —NR 75 —. (R 75 is a hydrogen atom or a substituent having 0 to 20 carbon atoms) represents a structure represented by, the amide structure, - (C = Q 4) -NR 76 - (Q 4 16 genera atom, R 76 Represents a hydrogen atom or a substituent having 0 to 20 carbon atoms, and the Schiff base structure represents a structure represented by -C = N-. Note that specific examples of the substituent having 0 to 20 carbon atoms in R 75 and R 76 correspond to the specific examples given as the substituent that Ar 1 to Ar 4 may have.
X1及びX2はそれぞれ同一であることが合成上の観点から好ましく、合成上の観点からはX1及びX2がエーテル構造であることがさらに好ましく、エーテル構造を形成する16属原子がそれぞれ酸素原子であることが特に好ましい。 X 1 and X 2 are preferably the same from the viewpoint of synthesis, and from the viewpoint of synthesis, X 1 and X 2 are more preferably an ether structure, and the 16 group atoms forming the ether structure are each Particularly preferred is an oxygen atom.
なお、X1及びX2は、隣接するポルフィリン環の「Ar1とAr3又はAr3同士」あるいは「Ar2とAr4又はAr4同士」と共有結合を介して結合する。 X 1 and X 2 are bonded via a covalent bond to “Ar 1 and Ar 3 or Ar 3 ′” or “Ar 2 and Ar 4 or Ar 4 ′” of adjacent porphyrin rings.
[Z]
Zは、置換基を有していてもよいアルキル基を表す。このアルキル基が有していても良い置換基の具体例としては、上述のAr1〜Ar4が有していても良い置換基としてあげられた具体例が相当する。なお、アルキル基の炭素鎖数(有していても良い置換基を除いたアルキル基の炭素数)は各ポルフィリン平面の二面角を10〜80度に固定できる長さに制限され、通常1〜12であり、好ましくは2〜8である。
[Z]
Z represents an alkyl group which may have a substituent. Specific examples of the substituent that the alkyl group may have correspond to the specific examples given as the substituent that Ar 1 to Ar 4 may have. The number of carbon chains of the alkyl group (the number of carbon atoms of the alkyl group excluding any substituents that may be present) is limited to a length that can fix the dihedral angle of each porphyrin plane to 10 to 80 degrees, and is usually 1 -12, preferably 2-8.
[ポルフィリン多量体の分子量]
以上に説明した一般式(1)で表されるポルフィリン多量体は、分子量増加に伴う2光子吸収特性低下防止の点から、分子量を該ポルフィリン多量体が有するポルフィリン環数で割った値が通常3,000以下であり、2,000以下であることが好ましく、1,500以下であることが特に好ましい。また、本発明の一般式(1)で表されるポルフィリン多量体は、通常水不溶性であることが好ましい。
[Molecular weight of porphyrin multimer]
The porphyrin multimer represented by the general formula (1) described above usually has a value obtained by dividing the molecular weight by the number of porphyrin rings of the porphyrin multimer from the viewpoint of preventing the decrease in the two-photon absorption characteristics accompanying the increase in the molecular weight. 2,000 or less, preferably 2,000 or less, particularly preferably 1,500 or less. The porphyrin multimer represented by the general formula (1) of the present invention is usually preferably insoluble in water.
[具体例]
本発明に係るポルフィリン系化合物の骨格構造の具体例を、図1(a)(b)に例示するが、本発明に係るポルフィリン系化合物は、本発明の要旨を越えない限りこれらに限定されるものではない。ここで、nは0〜13の整数を表す。なお、厳密に言えば、図1(a)(b)において示される各化合物のBnとCとの間のリンカーの位置が上にあるため、各化合物のBnのnの値は、偶数となる。このため、厳密に言えば、図1(a)(b)において示される各化合物のBnのnの値が奇数のもの、すなわち、BnとCとの間のリンカーの位置が下となる化合物は記載されていないことになる。しかし、図1(a)(b)はあくまで例示であり、nの値が奇数のものを排除するものではない。また、図1(a)(b)B−3,B−7,B−8は、リンカーを複数種有するが、このリンカーの順番は、ランダムにポルフィン環と結合し、特にその順番が限定されるものでない。
[Concrete example]
Specific examples of the skeleton structure of the porphyrin-based compound according to the present invention are illustrated in FIGS. 1 (a) and 1 (b), but the porphyrin-based compound according to the present invention is limited to these unless it exceeds the gist of the present invention. It is not a thing. Here, n represents an integer of 0 to 13. Strictly speaking, since the position of the linker between Bn and C of each compound shown in FIGS. 1A and 1B is on the upper side, the value of n of Bn of each compound is an even number. It becomes. Therefore, strictly speaking, as the value of n of B n of each compound shown in FIG. 1 (a) (b) is an odd number, i.e., the position of the linker between the B n and C is lower The compound will not be described. However, FIGS. 1A and 1B are merely examples, and do not exclude odd numbers. 1 (a) (b) B-3, B-7, and B-8 have a plurality of linkers. The order of the linkers is randomly bonded to the porphine ring, and the order is particularly limited. It is not something.
さらに、本発明に係るポルフィリン系化合物(1)の好ましい例として、式(2)、式(3)及び式(4)からなる部分構造、及び式(5)よりなるリンカーを有する構造について、式(2)、式(3)及び式(4)を形成する置換基の具体例を表1に示す。なお、Phはフェニル基を表す。また、式(5)よりなるリンカーの具体例としては、下記した(D−1)〜(D−6)があげられる。 Furthermore, as a preferable example of the porphyrin-based compound (1) according to the present invention, a partial structure consisting of the formula (2), the formula (3) and the formula (4), and a structure having a linker consisting of the formula (5) Specific examples of substituents that form (2), formula (3), and formula (4) are shown in Table 1. Ph represents a phenyl group. Specific examples of the linker comprising the formula (5) include the following (D-1) to (D-6).
本発明における環状ポルフィリン類は、例えば環A,B1〜Bn,C、L1〜Ln+1がそれぞれ同一である場合、以下の反応式<1>で示される反応にしたがった方法で合成できる。まず、5,15−無置換ポルフィリンもしくはその金属錯体(以下、反応式<1>中のP)を、既知の方法(銀塩などを用いた酸化)によってポルフィリンのメゾ位がそれぞれ直接結合した一連のポルフィリン多量体を得る。得られたポルフィリン多量体をゲル濾過クロマトグラフィーによって分離した後、共有結合の場合はリンカー(以下、反応式<1>中のL)をエーテル化やエステル化反応などによって結合することで、また、配位結合又は水素結合の場合は、リンカーLを化学量論量から溶媒量程度、無溶媒もしくは溶媒存在下で共存させることによって、それぞれのリンカーを有する無置換ポルフィリン多量体及びポルフィリン多量体金属錯体を得ることができる。 For example, when the rings A, B 1 to B n , C, and L 1 to L n + 1 are the same, the cyclic porphyrins in the present invention can be synthesized by a method according to the reaction represented by the following reaction formula <1>. First, 5,15-unsubstituted porphyrin or a metal complex thereof (hereinafter, P in the reaction formula <1>) is directly connected to the meso position of the porphyrin by a known method (oxidation using a silver salt or the like). To obtain a porphyrin multimer. After separating the obtained porphyrin multimer by gel filtration chromatography, in the case of a covalent bond, a linker (hereinafter, L in the reaction formula <1>) is bound by etherification or esterification reaction, In the case of a coordination bond or a hydrogen bond, an unsubstituted porphyrin multimer and a porphyrin multimeric metal complex each having a linker by allowing the linker L to coexist in a stoichiometric amount to a solvent amount in the absence of a solvent or in the presence of a solvent. Can be obtained.
なお、無置換ポルフィリン多量体を合成した後、金属塩と作用させることによりポルフィリン多量体金属錯体を合成することも可能であるが、多量化度が大きいほど金属塩との反応性が悪くなるため、ポルフィリン多量体金属錯体を合成する際にはあらかじめポルフィリン金属錯体単量体を用意しておくことが好ましい。 It is possible to synthesize a porphyrin multimeric metal complex by synthesizing an unsubstituted porphyrin multimer and then reacting with the metal salt, but the greater the degree of multimerization, the worse the reactivity with the metal salt. When synthesizing a porphyrin multimeric metal complex, it is preferable to prepare a porphyrin metal complex monomer in advance.
本発明より得られた新規ポルフィリン系化合物は、大きな2光子吸収断面積を有し、良好な2光子吸収特性を有する化合物であり、かつ700nm以降に吸収を有さないため、該化合物を用いることで、高性能な2光子吸収材料が提供できる。この場合の2光子吸収特性に優れるとは、該化合物の2光子吸収断面積が通常4,000GM以上、好ましくは10,000GM以上であることである。また、700nm以降に吸収を有さないとは、700nm以降の長波長域にモル吸光係数(ε)100以上の吸収を有さないことをいう。 The novel porphyrin-based compound obtained from the present invention is a compound having a large two-photon absorption cross section, good two-photon absorption characteristics, and no absorption after 700 nm. Thus, a high-performance two-photon absorption material can be provided. In this case, the excellent two-photon absorption property means that the two-photon absorption cross-sectional area of the compound is usually 4,000 GM or more, preferably 10,000 GM or more. Further, “having no absorption after 700 nm” means having no absorption with a molar extinction coefficient (ε) of 100 or more in a long wavelength region after 700 nm.
この化合物が高い2光子吸収断面積を有する理由の1つとしては、ポルフィリン環同士の2面角が90度を下回ることで、ポルフィリン環同士のπ共役効果が生まれたためであると推定される。 One of the reasons why this compound has a high two-photon absorption cross-sectional area is presumed to be that a π-conjugation effect between porphyrin rings was born when the dihedral angle between porphyrin rings was less than 90 degrees.
なお、本発明における2光子吸収材料中には、本発明に関わる新規ポルフィリン系化合物の1種が単独で含まれていても良いし、2種以上が混合して含まれていても良い。 In addition, in the two-photon absorption material in the present invention, one kind of novel porphyrin-based compounds related to the present invention may be contained alone, or two or more kinds may be mixed and contained.
本発明のポルフィリン系化合物を用いた2光子吸収材料は、該新規ポルフィリン系化合物単体もしくは該新規ポルフィリン系化合物を最低1種以上含む混合物の粉末状結晶をそのままの状態で、ブロックや粉末として、或いは、ヘキサン、トルエン、キシレン、塩化メチレン、クロロホルム、エーテル、テトラヒドロフラン、酢酸エチル、アセトン、2−ブタノン、メタノール、エタノール、トリフルオロメチルベンゼン、酢酸、トリエチルアミン等の溶媒、ポリマー、ゲル中に溶解又は分散させた液状物として、或いは、このような液状物を基板に塗布した後溶媒を除去して得られる薄膜状物として、各種用途に供することができる。 The two-photon absorption material using the porphyrin-based compound of the present invention is a block or powder as it is, with the powdery crystals of the novel porphyrin-based compound alone or a mixture containing at least one novel porphyrin-based compound as it is, or , Hexane, toluene, xylene, methylene chloride, chloroform, ether, tetrahydrofuran, ethyl acetate, acetone, 2-butanone, methanol, ethanol, trifluoromethylbenzene, acetic acid, triethylamine, etc. As a liquid material, or as a thin film material obtained by applying such a liquid material to a substrate and then removing the solvent, it can be used for various applications.
なお、2光子吸収材料が、本発明にかかる新規ポルフィリン系化合物を含んでいることは、該材料を分解、抽出等の処理を施した後、例えば、液体クロマトグラフィー−質量分析法(LC−MS)や核磁気共鳴スペクトル法(NMR)などで分析することにより確認することができる。 Note that the two-photon absorption material contains the novel porphyrin-based compound according to the present invention after the material is subjected to treatments such as decomposition and extraction, and then, for example, liquid chromatography-mass spectrometry (LC-MS ) Or nuclear magnetic resonance spectroscopy (NMR).
[その他の用途]
本発明における新規ポルフィリン系化合物のうち、特に好ましい例としてあげた式(2)、式(3)、式(4)及び式(5)からなる水素結合構造は、可逆的にポルフィリン環同士の二面角を制御できるため、2光子吸収材料用途の他、光メモリ用途、キラル認識材料用途、分子スイッチ用途等、種々の用途に利用可能である。
[Other uses]
Among the novel porphyrin-based compounds in the present invention, the hydrogen bond structure consisting of the formula (2), the formula (3), the formula (4) and the formula (5) mentioned as particularly preferred examples is reversibly formed between two porphyrin rings. Since the face angle can be controlled, it can be used for various applications such as optical memory applications, chiral recognition material applications, molecular switch applications, in addition to 2-photon absorption material applications.
[実施例]
まず、表1に示す化合物(C−1)〜(C−4)の合成について説明する。
[Example]
First, synthesis of the compounds (C-1) to (C-4) shown in Table 1 will be described.
<5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)の合成>
3,5−ジカルボキシメチル−4−ドデシルオキシベンズアルデヒド(アルドリッチ社製)4.65g(8.7mmol)と1,1−ジピリルメタン1.28g(8.7mmol)をCH2Cl2850mLに溶解し、これにトリフルオロ酢酸(TFA)0.67mL(8.8mmol)を窒素雰囲気下で添加した。そして、暗室で4時間攪拌した。次に、p−クロラニル5g(20mmol)を加え、一晩攪拌した。さらに、トリエチルアミン1.8mL(13mmol)を加え、反応液を15mLに濃縮し、シリカゲルカラムクロマトグラフィーで精製することによって無置換ポルフィリンを得た。得られた無置換ポルフィリンに過剰のZn(OAc)2(アルドリッチ社製)を加え、CH2Cl2/CH3OH混合溶媒(容積比 1/1)を加えて、1時間還流した。反応後、飽和NaHCO3水溶液で洗浄し、硫酸ナトリウムの存在下で水分を乾燥し、次いで上記混合溶媒を除去した。得られた残渣をカラムクロマトグラフィー(シリカゲル、ヘキサン/CH2Cl2=1/2から0/1へ連続的に変化させる)で精製し、クロロホルム/メタノール混合溶媒(容積比 1/1)で再結晶させ、紫色の亜鉛錯体1.3g(収率28%)を得た。化合物の同定は1H NMR及びTOF−MSにより行った。
<Synthesis of 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porfinato zinc (II)>
3.65 g (8.7 mmol) of 3,5-dicarboxymethyl-4-dodecyloxybenzaldehyde (manufactured by Aldrich) and 1.28 g (8.7 mmol) of 1,1-dipyrylmethane were dissolved in 850 mL of CH 2 Cl 2 . To this was added 0.67 mL (8.8 mmol) of trifluoroacetic acid (TFA) under a nitrogen atmosphere. And it stirred for 4 hours in the dark room. Next, 5 g (20 mmol) of p-chloranil was added and stirred overnight. Furthermore, 1.8 mL (13 mmol) of triethylamine was added, the reaction solution was concentrated to 15 mL, and purified by silica gel column chromatography to obtain unsubstituted porphyrin. Excess Zn (OAc) 2 (manufactured by Aldrich) was added to the resulting unsubstituted porphyrin, a CH 2 Cl 2 / CH 3 OH mixed solvent (volume ratio 1/1) was added, and the mixture was refluxed for 1 hour. After the reaction, the mixture was washed with a saturated aqueous NaHCO 3 solution, dried with water in the presence of sodium sulfate, and then the mixed solvent was removed. The obtained residue was purified by column chromatography (silica gel, hexane / CH 2 Cl 2 = continuously changed from 1/2 to 0/1), and re-purified with a chloroform / methanol mixed solvent (volume ratio 1/1). Crystallization gave 1.3 g (yield 28%) of a purple zinc complex. The compound was identified by 1 H NMR and TOF-MS.
・1H NMR(CDCl3) δ10.34(s,2H,meso−H),9.46(d,J=4.3Hz,4H,β−H),9.07(d,J=4.3Hz,4H,β−H),8.75(s,4H,Ar−H),4,37(t,J=6.4Hz,4H,OCH2),3.97(s,12H,COOMe),2.03(quin,J=7.0Hz,4H,CH2),1.55(m,4H,CH2),1.31−1.48(m,32H,CH2)
,0.90(t,J=6.4Hz,CH3,6H).
・Mass(MALDI−TOF):Obs.m/z=1125.8(M+1);Calc. for C64H76N4O10Zn,1124.5.
· 1 H NMR (CDCl 3) δ10.34 (s, 2H, meso-H), 9.46 (d, J = 4.3Hz, 4H, β-H), 9.07 (d, J = 4. 3 Hz, 4H, β-H), 8.75 (s, 4H, Ar—H), 4, 37 (t, J = 6.4 Hz, 4H, OCH 2 ), 3.97 (s, 12H, COOMe) , 2.03 (quin, J = 7.0 Hz, 4H, CH 2 ), 1.55 (m, 4H, CH 2 ), 1.31-1.48 (m, 32H, CH 2 )
, 0.90 (t, J = 6.4 Hz, CH 3 , 6H).
Mass (MALDI-TOF): Obs. m / z = 1125.8 (M + 1); Calc. for C 64 H 76 N 4 O 10 Zn, 1124.5.
<メゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)2量体及び3量体の合成>
5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)/クロロホルム2mMに、2当量のAgPF6/CH3CNを加え、3時間還流し、その後、アセトン及びNaHCO3水溶液を加えて反応を終了させた。有機層を分離し、NaHCO3水溶液で洗浄した後、シリカゲルカラムに吸着させて、CH2Cl2で溶出させた。そしてGPC(ゲル濾過クロマトグラフィー)で精製し、メゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)2量体及び3量体を得た。2量体(式(6)においてn=0))の収率は20%、3量体(式(6)においてn=1))の収率は10%、4量体(式(6)においてn=1))の収率は10%であった。化合物の同定は1H NMR及びTOF−MSにより行った。
<Synthesis of meso-meso bond 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porphinato zinc (II) dimer and trimer>
To 2mM 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porfinatozinc (II) / chloroform, 2 equivalents of AgPF 6 / CH 3 CN was added and refluxed for 3 hours, followed by acetone and NaHCO 3. Three aqueous solutions were added to terminate the reaction. The organic layer was separated, washed with aqueous NaHCO 3 solution, adsorbed on a silica gel column and eluted with CH 2 Cl 2 . And it refine | purified by GPC (gel filtration chromatography), and the meso-meso coupling | bonding 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porfinato zinc (II) dimer and trimer were obtained. The yield of the dimer (n = 0 in the formula (6)) is 20%, the yield of the trimer (n = 1 in the formula (6)) is 10%, and the tetramer (the formula (6)). The yield of n = 1)) was 10%. The compound was identified by 1 H NMR and TOF-MS.
(2量体のデータ)
・1H NMR(CDCl3) δ10.39(s,2H,meso−H),9.52(d,J=4.6Hz,4H,β−H),9.09(d,J=4.6Hz,4H,β−H),8.76(s,8H,Ar−H),8.64(d,J=4.6Hz,4H,β−H),8.11(d,J=4.6Hz,4H,β−H),4.28(t,J=7.0Hz,8H,OCH2),3.91(s,24H,COOMe),1.95(quin,J=7.5Hz,8H,CH2),1.55(m,8H,CH2),1.44(m,8H,CH2),1.25−1.36(m,56H,CH2),and0.87(t,J=7.0Hz,12H,CH3).
・Mass(MALDI−TOF):Obs.2251.1;Cald. for C128H150N8O20Zn2,2247.0.
(Dimer data)
· 1 H NMR (CDCl 3) δ10.39 (s, 2H, meso-H), 9.52 (d, J = 4.6Hz, 4H, β-H), 9.09 (d, J = 4. 6 Hz, 4H, β-H), 8.76 (s, 8H, Ar-H), 8.64 (d, J = 4.6 Hz, 4H, β-H), 8.11 (d, J = 4) .6 Hz, 4H, β-H), 4.28 (t, J = 7.0 Hz, 8H, OCH 2 ), 3.91 (s, 24H, COOMe), 1.95 (quin, J = 7.5 Hz) , 8H, CH 2), 1.55 (m, 8H, CH 2), 1.44 (m, 8H, CH 2), 1.25-1.36 (m, 56H, CH 2), and0.87 (T, J = 7.0 Hz, 12H, CH 3 ).
Mass (MALDI-TOF): Obs. 2251.1; Cald. for C 128 H 150 N 8 O 20 Zn 2 , 2247.0.
(3量体のデータ)
・1H NMR(CDCl3) δ10.47(s,2H,meso−H),9.57(d,J=4.6Hz,4H,β−H),9.13(d,J=4.6Hz,4H,β−H),8.78(s,8H,Ar−H),8.74(d,J=4.6Hz,4H,β−H),8.70(s,4H,Ar−H),8.65(d,J=4.6Hz,4H,β−H),8.27(d,J=4.6Hz,4H,β−H),8.16(d,J=4.6Hz,4H,β−H),4.29(t,J=6.4Hz,8H,OCH2),4.13(t,J=6.4Hz,4H,OCH2),3.91(s,24H,COOMe),3.79(s,12H,COOMe),1.97(quin,J=6.8Hz,8H,CH2),1.82(quin,J=6.9Hz,4H,CH2),1.56(m,8H,CH2),1.16−1.41(m,100H,CH2),0.87(t,J=6.4Hz,12H,CH3),and 0.78(t,J=6.4Hz,6H,CH3).
・Mass(MALDI−TOF):Obs.3370.8;Cald. for C192H224N12O30Zn3,3369.4.
(Trimer data)
1 H NMR (CDCl 3 ) δ 10.47 (s, 2H, meso-H), 9.57 (d, J = 4.6 Hz, 4H, β-H), 9.13 (d, J = 4. 6 Hz, 4H, β-H), 8.78 (s, 8H, Ar-H), 8.74 (d, J = 4.6 Hz, 4H, β-H), 8.70 (s, 4H, Ar) -H), 8.65 (d, J = 4.6 Hz, 4H, β-H), 8.27 (d, J = 4.6 Hz, 4H, β-H), 8.16 (d, J = 4.6 Hz, 4H, β-H), 4.29 (t, J = 6.4 Hz, 8H, OCH 2 ), 4.13 (t, J = 6.4 Hz, 4H, OCH 2 ), 3.91. (S, 24H, COOMe), 3.79 (s, 12H, COOMe), 1.97 (quin, J = 6.8 Hz, 8H, CH 2 ), 1.82 (quin, J = 6.9 Hz, 4 H, CH 2), 1.56 ( m, 8H, CH 2), 1.16-1.41 (m, 100H, CH 2), 0.87 (t, J = 6.4Hz, 12H, CH 3 ), And 0.78 (t, J = 6.4 Hz, 6H, CH 3 ).
Mass (MALDI-TOF): Obs. 3370.8; Cald. for C 192 H 224 N 12 O 30 Zn 3 , 3369.4.
<メゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)4量体の合成>
原料としてメゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)2量体を用いた以外は、上記のカップリング反応と同様の反応を行い合成した。収率は8%であった。化合物の同定は1H NMR及びTOF−MSにより行った。
<Synthesis of meso-meso bond 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porphinatozinc (II) tetramer>
Synthesis is performed by performing the same reaction as the above coupling reaction except that meso-meso bond 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porfinatozinc (II) dimer is used as a raw material. did. The yield was 8%. The compound was identified by 1 H NMR and TOF-MS.
・1H NMR(CDCl3) δ10.35(s,2H,meso−H),9.50(d,J=4.6Hz,4H,β−H),9.07(d,J=4.6Hz,4H,β−H),8.77(s,8H,Ar−H),8.71(s,8H,Ar−H),8.60(d,J=4.6Hz,4H,β−H),8.58(d,J=4.6Hz,4H,β−H),8.52(d,J=4.6Hz,β−H),8.09(br,4H,β−H),8.06(br,4H,β−H),7.93(br,4H,β−H),4.31(t,J=6.4Hz,8H,OCH2),4.17(t,J=6.4Hz,8H,OCH2),3.93(s,24H,COOMe),3.83(s,24H,COOMe),1.96(m,8H,CH2),1.81(m,8H,CH2),1.55(m,8H,CH2),1.19−1.43(m,136H,CH2),0.87(t,J=6.4Hz,12H,CH3),and0.81(t,J=6.4Hz,12H,CH3).
・Mass(MALDI−TOF):Obs.4490.8;Calc. for C256H298N16O40Zn4,,4491.9
1 H NMR (CDCl 3 ) δ 10.35 (s, 2H, meso-H), 9.50 (d, J = 4.6 Hz, 4H, β-H), 9.07 (d, J = 4. 6 Hz, 4H, β-H), 8.77 (s, 8H, Ar-H), 8.71 (s, 8H, Ar-H), 8.60 (d, J = 4.6 Hz, 4H, β -H), 8.58 (d, J = 4.6 Hz, 4H, β-H), 8.52 (d, J = 4.6 Hz, β-H), 8.09 (br, 4H, β- H), 8.06 (br, 4H, β-H), 7.93 (br, 4H, β-H), 4.31 (t, J = 6.4 Hz, 8H, OCH 2 ), 4.17. (T, J = 6.4 Hz, 8H, OCH 2 ), 3.93 (s, 24H, COOMe), 3.83 (s, 24H, COOMe), 1.96 (m, 8H, CH 2 ), 1 .81 (m, 8 , CH 2), 1.55 (m , 8H, CH 2), 1.19-1.43 (m, 136H, CH 2), 0.87 (t, J = 6.4Hz, 12H, CH 3) , And 0.81 (t, J = 6.4 Hz, 12H, CH 3 ).
Mass (MALDI-TOF): Obs. 4490.8; Calc. for C 256 H 298 N 16 O 40 Zn 4 ,, 4491.9
<メゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)8量体の合成>
原料としてメゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)4量体を用いた以外は、上記のカップリング反応と同様の反応を行い合成した。収率は8%であった。化合物の同定は1H NMR及びTOF−MSにより行った。
<Synthesis of meso-meso bond 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porphinato zinc (II) octamer>
Synthesis is performed by performing the same reaction as the above coupling reaction except that meso-meso bond 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porfinatozinc (II) tetramer is used as a raw material. did. The yield was 8%. The compound was identified by 1 H NMR and TOF-MS.
・1H NMR(CDCl3) δ10.48(s,2H,β−H),9.59(d,4.6Hz,4H,β−H),9.15(d,4.6Hz,4H,β−H),8.77−8.40(m,56H,Ar−H and β−H),8.70(d,4.6Hz,4H,β−H),8.38(m,20H,β−H),8.31(d,4.6Hz,4H,β−H),8.20(d,4.6Hz,4H,β−H),4.31(t,J=6.4Hz,8H,OCH2),4.22(m,24H,OCH2),3.84−3.88(m,96H,COOMe),1.95(m,8H,CH2),1.88(m,24H,CH2),1.15−1.59(m,288H,CH2),0.87(t,J=6.4Hz,12H,CH3),and 0.82(m,36H,CH3).
・Mass(MALDI−TOF):Obs.8983.1;Calc. for C512H594N32O80Zn8,, 8981.7.
· 1 H NMR (CDCl 3) δ10.48 (s, 2H, β-H), 9.59 (d, 4.6Hz, 4H, β-H), 9.15 (d, 4.6Hz, 4H, β-H), 8.77-8.40 (m, 56H, Ar-H and β-H), 8.70 (d, 4.6 Hz, 4H, β-H), 8.38 (m, 20H) , Β-H), 8.31 (d, 4.6 Hz, 4H, β-H), 8.20 (d, 4.6 Hz, 4H, β-H), 4.31 (t, J = 6. 4Hz, 8H, OCH 2), 4.22 (m, 24H, OCH 2), 3.84-3.88 (m, 96H, COOMe), 1.95 (m, 8H, CH 2), 1.88 (m, 24H, CH 2) , 1.15-1.59 (m, 288H, CH 2), 0.87 (t, J = 6.4Hz, 12H, CH 3), and 0.82 (m 36H, CH 3).
Mass (MALDI-TOF): Obs. 8983.1; Calc. for C 512 H 594 N 32 O 80 Zn 8 ,, 8981.7.
<メゾ−メゾ結合5,15−(3,5−ジカルボキシ−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)オリゴマー(化合物(C−1))の合成>
メゾ−メゾ結合5,15−(3,5−ジメトキシカルボニル−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)2量体、3量体、4量体、8量体の20mgをそれぞれTHF6mLに溶解し、12N NaOH2mL、及びCH3OH4mlを加えて、一晩撹拌した。混合物に純水を加え、1N HCl水溶液で酸性にし、ジエチルエーテルを加えて抽出した。有機層を取り出して、水で洗浄し、無水硫酸ナトリウムの存在下で乾燥後、上記混合溶媒を除去した。得られた残渣をTHF/ジエチルエーテル(2量体の場合)及びTHF/ヘプタン(3量体、4量体、8量体の場合)で再結晶させ、一連のメゾ−メゾ結合5,15−(3,5−ジカルボキシ−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)オリゴマーを得た。化合物の収率は、2量体で67%、3量体で78%、4量体で91%、8量体で64%であった。化合物の同定は1H NMR及びTOF−MSにより行った。なお、ここで合成したメゾ−メゾ結合5,15−(3,5−ジカルボキシ−4−ドデシルオキシフェニル)ポルフィナト亜鉛(II)2量体が表1における化合物(C−1)、3量体が化合物(C−2)、4量体が化合物(C−3)、8量体が化合物(C−4)である。得られた2量体〜8量体の隣接するポルフィン環同士の二面角は、90°で、リンカー(D−1)を加えることにより、下記の表2に記載の通り、ポルフィン環同士の二面角は、72°となった。
<Synthesis of meso-meso bond 5,15- (3,5-dicarboxy-4-dodecyloxyphenyl) porfinato zinc (II) oligomer (compound (C-1))>
Dissolve 20 mg of meso-meso bond 5,15- (3,5-dimethoxycarbonyl-4-dodecyloxyphenyl) porfinatozinc (II) dimer, trimer, tetramer and octamer in 6 mL of THF, respectively. , 12N NaOH 2 mL, and CH 3 OH 4 ml were added and stirred overnight. Pure water was added to the mixture, acidified with 1N aqueous HCl, and extracted with diethyl ether. The organic layer was taken out, washed with water, dried in the presence of anhydrous sodium sulfate, and then the mixed solvent was removed. The resulting residue is recrystallized with THF / diethyl ether (in the case of dimer) and THF / heptane (in the case of trimer, tetramer and octamer), and a series of meso-meso linkages 5,15- (3,5-dicarboxy-4-dodecyloxyphenyl) porfinato zinc (II) oligomer was obtained. The yield of the compound was 67% for the dimer, 78% for the trimer, 91% for the tetramer, and 64% for the octamer. The compound was identified by 1 H NMR and TOF-MS. The meso-meso bond 5,15- (3,5-dicarboxy-4-dodecyloxyphenyl) porphynatozinc (II) dimer synthesized here is the compound (C-1) or trimer in Table 1. Is the compound (C-2), the tetramer is the compound (C-3), and the octamer is the compound (C-4). The dihedral angle between adjacent porphine rings of the obtained dimer to octamer is 90 °, and by adding a linker (D-1), as shown in Table 2 below, The dihedral angle was 72 °.
(化合物(C−1))
・1H NMR(CD3OD) δ10.37(s,2H,meso−H),9.51(d,J=4.6Hz,4H,β−H),9.01(d,J=4.6Hz,4H,β−H),8.69(s,8H,Ar−H),8.56(d,J=4.6Hz,4H,β−H),8.10(d,J=4.6Hz,4H,β−H),4.28(t,J=6.5Hz,8H,OCH2),1.89(quin,J=6.4Hz,8H,CH2),1.51(quin,J=6.4Hz,8H,CH2),1.19−1.29(m,64H,CH2),
and 0.80(t,J=6.6Hz,12H,CH3).
・Mass(MALDI−TOF):Obs.2140.5;Calc. for C120H134N8O20Z2, 2134.8
(Compound (C-1))
1 H NMR (CD 3 OD) δ 10.37 (s, 2H, meso-H), 9.51 (d, J = 4.6 Hz, 4H, β-H), 9.01 (d, J = 4) .6 Hz, 4H, β-H), 8.69 (s, 8H, Ar-H), 8.56 (d, J = 4.6 Hz, 4H, β-H), 8.10 (d, J = 4.6 Hz, 4H, β-H), 4.28 (t, J = 6.5 Hz, 8H, OCH 2 ), 1.89 (quin, J = 6.4 Hz, 8H, CH 2 ), 1.51 (quin, J = 6.4Hz, 8H , CH 2), 1.19-1.29 (m, 64H, CH 2),
and 0.80 (t, J = 6.6 Hz, 12H, CH 3 ).
Mass (MALDI-TOF): Obs. 2140.5; Calc. for C 120 H 134 N 8 O 20 Z 2 , 214.8
(化合物(C−2))
・1H NMR(CD3Cl3/THF−d8=10:1) σ10.26(s,2H,meso−H),9.42(d,J=4.6Hz,4H,β−H),9.02(d,partially overlapped with Ar−H,4H,β−H),9.01(s,8H,Ar−H),9.00(s,4H,Ar−H),8.61(d,J=4.6Hz,4H,β−H),8.57(d,J=4.6Hz,4H,β−H),8.15(d,J=4.6Hz,4H,β−H),8.04(d,J=4.6Hz,4H,β−H),4.38(t,J=6.4Hz,8H,OCH2),4.23(t,J=6.4Hz,4H,OCH2),1.96(m,8H,CH2),1.81(m,4H,CH2),1.10−1.35(m,108H,CH2),0.80(t,J=6.5Hz,12H,CH3), and 0.78(t,J=6.6Hz,6H,CH3).
・Mass(MALDI−TOF):Obs.3203.9;Calc. for C180H200N12O30Zn3, 3201.2.
(Compound (C-2))
1 H NMR (CD 3 Cl 3 / THF-d 8 = 10: 1) σ 10.26 (s, 2H, meso-H), 9.42 (d, J = 4.6 Hz, 4H, β-H) 9.02 (d, partially overlapped with Ar-H, 4H, β-H), 9.01 (s, 8H, Ar-H), 9.00 (s, 4H, Ar-H), 8.61. (D, J = 4.6 Hz, 4H, β-H), 8.57 (d, J = 4.6 Hz, 4H, β-H), 8.15 (d, J = 4.6 Hz, 4H, β -H), 8.04 (d, J = 4.6 Hz, 4H, β-H), 4.38 (t, J = 6.4 Hz, 8H, OCH 2 ), 4.23 (t, J = 6) .4 Hz, 4 H, OCH 2 ), 1.96 (m, 8 H, CH 2 ), 1.81 (m, 4 H, CH 2 ), 1.10-1.35 (m, 108 H, CH 2), 0.80 ( t, J = 6.5Hz, 12H, CH 3), and 0.78 (t, J = 6.6Hz, 6H, CH 3).
Mass (MALDI-TOF): Obs. 3203.9; Calc. for C 180 H 200 N 12 O 30 Zn 3 , 3201.2.
(化合物(C−3))
・1H NMR(CDCl3/THF−d8=10:1) δ10.28(s,2H,meso−H),9.42(d,J=4.6Hz,4H,β−H),8.97(d,partially overlapped with Ar−H,4H,β−H),8.98(s,8H,Ar−H),8.94 (s,8H,Ar−H),8.59(d,J=4.6Hz,4H,β−H),8.58(d,J=4.6Hz,4H,β−H),8.51(d,J=4.6Hz,4H,β−H),8.18(d,J=4.6Hz,4H,β−H),8.15(d,J=4.6Hz,4H,β−H),8.03(d,J=4.6Hz,4H,β−H),4.41(t,J=6.6Hz,8H,OCH2),4.27(t,J=6.7Hz,8H,OCH2),1.96(m,8H,CH2),1.55(m,8H,CH2),1.12−1.50(m,144H,CH2),0.80(t,J=6.5Hz,12H,CH3), and 0.74(t,J=6.5Hz,12H,CH3).
・Mass(MALDI−TOF):Obs.4271.3,Calc. for C240H266N16O40Zn4, 4267.7.
(Compound (C-3))
1 H NMR (CDCl 3 / THF-d 8 = 10: 1) δ 10.28 (s, 2H, meso-H), 9.42 (d, J = 4.6 Hz, 4H, β-H), 8 97 (d, partially overlapped with Ar-H, 4H, β-H), 8.98 (s, 8H, Ar-H), 8.94 (s, 8H, Ar-H), 8.59 (d , J = 4.6 Hz, 4H, β-H), 8.58 (d, J = 4.6 Hz, 4H, β-H), 8.51 (d, J = 4.6 Hz, 4H, β-H) ), 8.18 (d, J = 4.6 Hz, 4H, β-H), 8.15 (d, J = 4.6 Hz, 4H, β-H), 8.03 (d, J = 4. 6Hz, 4H, β-H) , 4.41 (t, J = 6.6Hz, 8H, OCH 2), 4.27 (t, J = 6.7Hz, 8H, OCH 2), 1. 6 (m, 8H, CH 2 ), 1.55 (m, 8H, CH 2), 1.12-1.50 (m, 144H, CH 2), 0.80 (t, J = 6.5Hz, 12H, CH 3 ), and 0.74 (t, J = 6.5 Hz, 12H, CH 3 ).
Mass (MALDI-TOF): Obs. 4271.3, Calc. for C 240 H 266 N 16 O 40 Zn 4 , 4267.7.
(化合物(C−4))
・1H NMR(CDCl3/THF−d8=10:1) δ10.28(s,2H,meso−H),9.42(d,J=4.3Hz,4H,β−H),8.94−8.99(m,36H,Ar−H and β−H),8.60−8.63(m,24H,β−H),8.52(d,J=4.6Hz,4H,β−H),8.19−8.22(m,20H,β−H),8.15(d,J=4.6Hz,4H,β−H),8.03(d,J=4.6Hz,4H,β−H),4.41(t,J=6.4Hz,8H,OCH2),4.32(m,24H,OCH2),2.02(m,8H,CH2),1.10−1.59(m,312H,CH2),and0.75−0.80(m,48H,CH3).
・Mass(MALDI−TOF):Obs.8539.5,Calc. for C480H530N32O80Zn8 8533.3.
(Compound (C-4))
1 H NMR (CDCl 3 / THF-d 8 = 10: 1) δ 10.28 (s, 2H, meso-H), 9.42 (d, J = 4.3 Hz, 4H, β-H), 8 .94-8.99 (m, 36H, Ar-H and β-H), 8.60-8.63 (m, 24H, β-H), 8.52 (d, J = 4.6 Hz, 4H) , Β-H), 8.19-8.22 (m, 20H, β-H), 8.15 (d, J = 4.6 Hz, 4H, β-H), 8.03 (d, J = 4.6 Hz, 4H, β-H), 4.41 (t, J = 6.4 Hz, 8H, OCH 2 ), 4.32 (m, 24H, OCH 2 ), 2.02 (m, 8H, CH 2), 1.10-1.59 (m, 312H , CH 2), and0.75-0.80 (m, 48H, CH 3).
Mass (MALDI-TOF): Obs. 859.5, Calc. for C 480 H 530 N 32 O 80 Zn 8 853.3.
次に、化合物(B−1)(n=1、3量体)の合成について説明する。
<中間体(B’−1)の合成>
<Synthesis of Intermediate (B′-1)>
常法で合成した5,10−ビス(3−ヒドロキシフェニル)ポルフィン(290mg)及び1,4−ジブロモブタン(2.8ml)、炭酸カルシウム(4.0g)の混合物をアセトン(300ml)中で10時間加熱還流した。反応液を濃縮した後、塩化メチレンで抽出し、水洗した。溶媒を減圧条件下で留去した後塩化メチレン/メタノールで再結晶を行うことにより目的化合物(287mg、収率61%)を得た。化合物の同定は1H NMR及びMALDI TOF−MSにより行った。 A mixture of 5,10-bis (3-hydroxyphenyl) porphine (290 mg), 1,4-dibromobutane (2.8 ml) and calcium carbonate (4.0 g) synthesized in a conventional manner was added in acetone (300 ml) to 10 Heated to reflux for hours. The reaction mixture was concentrated, extracted with methylene chloride, and washed with water. The solvent was distilled off under reduced pressure, and then recrystallization was carried out with methylene chloride / methanol to obtain the desired compound (287 mg, yield 61%). The compound was identified by 1 H NMR and MALDI TOF-MS.
・1H NMR(CDCl3) σ10.31(s,2H,meso−H),9.38(d,J=4.6Hz,4H,β−H),9.11(d,J=4.6Hz,4H,β−H),7.85(d,J=7.3Hz,2H,Ar−H),7.81(br,2H,Ar−H),7.68(t,J=7.3Hz,2H,Ar−H),7.34(dd,J=7.3,1.9Hz,2H,Ar−H),4.22(t、J=5.9Hz,4H,CH2), 3.53(t,J=6.4Hz,4H,CH2),2.16and2.07(each m,CH2,4H×2),−3.14(br.s,2H,NH)
・Mass(MALDI−TOF):Obs.m/z=758.49;Cald. for C40H36Br2N4O2 762.12.
· 1 H NMR (CDCl 3) σ10.31 (s, 2H, meso-H), 9.38 (d, J = 4.6Hz, 4H, β-H), 9.11 (d, J = 4. 6 Hz, 4H, β-H), 7.85 (d, J = 7.3 Hz, 2H, Ar-H), 7.81 (br, 2H, Ar-H), 7.68 (t, J = 7) .3 Hz, 2H, Ar-H), 7.34 (dd, J = 7.3, 1.9 Hz, 2H, Ar-H), 4.22 (t, J = 5.9 Hz, 4H, CH2), 3.53 (t, J = 6.4 Hz, 4H, CH 2 ), 2.16 and 2.07 (each m, CH 2 , 4H × 2), −3.14 (br.s, 2H, NH)
Mass (MALDI-TOF): Obs. m / z = 758.49; Cald. for C 40 H 36 Br 2 N 4 O 2 762.12.
<中間体(B’−2)の合成>
中間体(B’−1)(165mg)、5−(3,5−ジ−tert−ブチルフェニル)−15−(3−ヒドロキシフェニル)ポルフィン(257mg)及び炭酸カリウム(0.89g)の混合物をDMF(15ml)中で12時間130−140℃で処理した。反応液を塩化メチレンで抽出し、水洗した。有機層を硫酸ナトリウムで乾燥し、減圧条件下で溶媒を留去した後、シリカゲルカラムクロマトグラフィーで精製することでフリーベースポルフィリン3量体を得た。該化合物をクロロホルム中酢酸亜鉛で処理し、反応混合物を水洗した後塩化メチレン/メタノールで再結晶することで目的化合物(214mg、52%)を得た。同定は1H NMR及びMALDI−TOF MSにより行った。 A mixture of intermediate (B′-1) (165 mg), 5- (3,5-di-tert-butylphenyl) -15- (3-hydroxyphenyl) porphine (257 mg) and potassium carbonate (0.89 g) Treated in DMF (15 ml) for 12 hours at 130-140 ° C. The reaction solution was extracted with methylene chloride and washed with water. The organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a free base porphyrin trimer. The compound was treated with zinc acetate in chloroform, and the reaction mixture was washed with water and then recrystallized from methylene chloride / methanol to obtain the desired compound (214 mg, 52%). Identification was performed by 1 H NMR and MALDI-TOF MS.
・1H NMR (CDCl3) σ 10.17, 10.16 (each s,4H,meso−H),10.00,9.99(each s,2H,meso−H),9.36,9.29,9.21,9.17,9.16,and 9.11(each m,4H×6,β−H),8.11(m,4H,Ar−H),7.77−7.84(m,10H,Ar−H),7.59(m,4H,Ar−H),7.34(m,4H,Ar−H),4.30(m,8H,CH2),2.17(m,8H,CH2),1.55(m,18H,tert−butyl).
・Mass (MALDI−TOF):Obs.m/z=1968.47(M+);Cald. for C120H104N12O4Zn3 1968.02.
· 1 H NMR (CDCl 3) σ 10.17, 10.16 (each s, 4H, meso-H), 10.00,9.99 (each s, 2H, meso-H), 9.36,9 .29, 9.21, 9.17, 9.16, and 9.11 (each m, 4H × 6, β-H), 8.11 (m, 4H, Ar—H), 7.77-7 .84 (m, 10H, Ar- H), 7.59 (m, 4H, Ar-H), 7.34 (m, 4H, Ar-H), 4.30 (m, 8H, CH 2), 2.17 (m, 8H, CH 2 ), 1.55 (m, 18H, tert-butyl).
Mass (MALDI-TOF): Obs. m / z = 1968.47 (M + ); Cald. for C 120 H 104 N 12 O 4 Zn 3 1968.02.
<化合物(B−1)(n=1)の合成>
中間体(B’−2)(100mg)のクロロホルム(1L)溶液に、六フッ化リン酸銀のアセトニトリル溶液(0.12M、0.85ml)を加え、遮光条件で20分撹拌した。反応混合物を水洗し、硫酸ナトリウムで乾燥させた後減圧条件下で溶媒を留去した。得られた残渣にクロロホルム(1L)を加えて溶解させた後、六フッ化リン酸銀のアセトニトリル溶液(0.12M、0.85ml)を加え、遮光条件で20分撹拌した。反応混合物を水洗し、硫酸ナトリウムで乾燥させた後減圧条件下で溶媒を留去した。得られた残渣をゲル濾過クロマトグラフィー及びシリカゲルカラムクロマトグラフィーで精製し、塩化メチレン/メタノールで再結晶させることで、目的化合物(10mg、収率10%)を得た。同定は1H NMR、MALDI−TOF MS及びX線結晶構造解析(図2(a)(b))により行った。
X線結晶構造解析から、該化合物の隣接するポルフィリン環同士の二面角は64度であった。該化合物のクロロホルム中での紫外可視吸収スペクトルを図3(a)に示す。800nmにおける吸収強度はゼロであった。
<Synthesis of Compound (B-1) (n = 1)>
To a solution of intermediate (B′-2) (100 mg) in chloroform (1 L) was added silver hexafluorophosphate in acetonitrile (0.12 M, 0.85 ml), and the mixture was stirred for 20 minutes under light shielding conditions. The reaction mixture was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. Chloroform (1 L) was added to the resulting residue for dissolution, and then a silver hexafluorophosphate acetonitrile solution (0.12 M, 0.85 ml) was added, followed by stirring for 20 minutes under light-shielding conditions. The reaction mixture was washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by gel filtration chromatography and silica gel column chromatography, and recrystallized from methylene chloride / methanol to obtain the target compound (10 mg, yield 10%). Identification was performed by 1 H NMR, MALDI-TOF MS, and X-ray crystal structure analysis (FIGS. 2A and 2B).
From the X-ray crystal structure analysis, the dihedral angle between adjacent porphyrin rings of the compound was 64 degrees. The ultraviolet-visible absorption spectrum of the compound in chloroform is shown in FIG. The absorption intensity at 800 nm was zero.
・1H NMR(CDCl3) σ 10.41(s,2H,meso−H),9.55(d,J=4.6Hz,2H,β−H),9.53(d,J=4.1Hz,2H,β−H),9.51(d,J=4.6Hz,2H,β−H),9.49(d,J=4.6Hz,2H,β−H),9.47(d,J=4.6Hz,2H,β−H),9.26(d,J=4.1Hz,2H,β−H),9.17(d,J=4.1Hz,2H,β−H),9.05(d,J=4.1Hz,2H,β−H),8.53(d,J=4.6Hz,2H,β−H),8.43(d,J=4.6Hz,2H,β−H),8.39(m,2H,Ar−H),8.24(d,J=6.9Hz,2H,Ar−H),8.09(m,2H,Ar−H),8.08(d,J=6.9Hz,2H,Ar−H),7.81(m,2H,Ar−H),7.75(br.s,2H,Ar−H),7.71(t,J=6.9Hz,2H,Ar−H),7.65(br.s,2H,Ar−H),7.55(t,J=6.9Hz,2H,Ar−H),7.41(d,J=4.6Hz,2H,β−H),7.27(dd,J=8.0 and 1.9Hz,2H,Ar−H),7.19(dd,J=8.0 and 1.9Hz,2H,Ar−H),7.11(d,J=4.6Hz,2H,β−H),4.17(m,4H,CH2),4.04 and 3.96(each m,2H×2,CH2),2.21 and 2.06(each m,4H×2,CH2),1.61 and 1.49(each 2,18H×2,tert−butyl).
・Mass(MALDI−TOF):Obs.m/z=1966.35(M+1),Cald.for C120H100N12O4Zn3 1964.59.
· 1 H NMR (CDCl 3) σ 10.41 (s, 2H, meso-H), 9.55 (d, J = 4.6Hz, 2H, β-H), 9.53 (d, J = 4 .1 Hz, 2H, β-H), 9.51 (d, J = 4.6 Hz, 2H, β-H), 9.49 (d, J = 4.6 Hz, 2H, β-H), 9. 47 (d, J = 4.6 Hz, 2H, β-H), 9.26 (d, J = 4.1 Hz, 2H, β-H), 9.17 (d, J = 4.1 Hz, 2H, β-H), 9.05 (d, J = 4.1 Hz, 2H, β-H), 8.53 (d, J = 4.6 Hz, 2H, β-H), 8.43 (d, J = 4.6 Hz, 2H, β-H), 8.39 (m, 2H, Ar-H), 8.24 (d, J = 6.9 Hz, 2H, Ar-H), 8.09 (m, 2H, Ar-H), 8.08 (d, J = 6.9 Hz, 2 H, Ar-H), 7.81 (m, 2H, Ar-H), 7.75 (br. S, 2H, Ar-H), 7.71 (t, J = 6.9 Hz, 2H, Ar -H), 7.65 (br.s, 2H, Ar-H), 7.55 (t, J = 6.9 Hz, 2H, Ar-H), 7.41 (d, J = 4.6 Hz, 2H, β-H), 7.27 (dd, J = 8.0 and 1.9 Hz, 2H, Ar-H), 7.19 (dd, J = 8.0 and 1.9 Hz, 2H, Ar- H), 7.11 (d, J = 4.6 Hz, 2H, β-H), 4.17 (m, 4H, CH 2 ), 4.04 and 3.96 (each m, 2H × 2, CH 2 ), 2.21 and 2.06 (each m, 4H × 2, CH 2 ), 1.61 and 1.49 (each 2, 18H × 2, tert-butyl).
Mass (MALDI-TOF): Obs. m / z = 1966.35 (M + 1), Cald. for C 120 H 100 N 12 O 4 Zn 3 1964.59.
(実施例1〜4)
[二光子吸収断面積の評価]
上記の方法で得られた化合物4.3×10−6Mの化合物(C−1)溶液、2.7×10−6Mの化合物(C−2)溶液、2.0×10−6Mの化合物(C−3)溶液、及び9.8×10−7Mの化合物(C−4)溶液(いずれも、溶媒はトルエン/THF=9/1の混合溶媒を使用)に、リンカーである化合物(D−1)の6.03×10−3M溶液(溶媒はトルエン/THF=9/1の混合溶媒を使用。)を混合した。それぞれの紫外可視吸収スペクトルを、図3(b)〜図3(e)に示す。いずれの吸収スペクトルにおいても、800nmにおける吸収強度はゼロであった。それぞれの混合物の二光子吸収断面積を、下記に示す方法にて測定した。
(Examples 1-4)
[Evaluation of two-photon absorption cross section]
Compound 4.3 × 10 −6 M compound (C-1) solution obtained by the above method, 2.7 × 10 −6 M compound (C-2) solution, 2.0 × 10 −6 M The compound (C-3) solution and the 9.8 × 10 −7 M compound (C-4) solution (both using a mixed solvent of toluene / THF = 9/1) are linkers. A 6.03 × 10 −3 M solution of the compound (D-1) (a solvent using a mixed solvent of toluene / THF = 9/1) was mixed. Each ultraviolet-visible absorption spectrum is shown in FIG. 3 (b) to FIG. 3 (e). In any absorption spectrum, the absorption intensity at 800 nm was zero. The two-photon absorption cross section of each mixture was measured by the method shown below.
二光子吸収断面積の評価はGuang S. He, Lixiang Yuan, Ning Cheng, Jayant D. Bhawalkar, Paras N. Prasad, Lawrence L. Brott, Stephen J. Clarson, Bruce A. Reinhardt, J. Opt. Soc. Am. B Vol.14, No.5(1997)pp.1079−1087記載の方法を参考にして行った。測定システム概略図を図4に示す。 The evaluation of the two-photon absorption cross section is described by Guang S. He, Lixiang Yuan, Ning Cheng, Jayant D. Bhawalkar, Paras N .; Prasad, Lawrence L. Brott, Stephen J. et al. Clarkson, Bruce A. Reinhardt, J.M. Opt. Soc. Am. B Vol. 14, no. 5 (1997) pp. 5-7. This was carried out with reference to the method described in 1079-1087. A schematic diagram of the measurement system is shown in FIG.
なお、図中の「Laser」は、チタンサファイアレーザであり、カントロニクス(Quantronix)社製:インテグラ(Integra)を用いた。また、「PD」は、フォトディテクタを意味し、ニューフォーカス(NewFocus)社製:円筒型ディテクターMODEL 818−SLを用いた。さらに、「Amp.」は、増幅器を意味し、スタンフォードリサーチシステム(STANFORD RESEARCH SYSTEMS)社製:ローノイズカレントプリアンプリファイア(LOW−NOISE CURRENT PREAMPLIFIER)MODEL SR570とゲーティッドインテグレータ&ボックスカーアベレージャ(GATED INTEGRATOR & BOXCAR AVERAGER)MODEL SR250を用いた。また、「BS」はビームスプリッタを意味し、「Quarts cell」は、石英製の試料セルを意味する。さらに、「PC」はパーソナルコンピューターを意味する。 In addition, "Laser" in a figure is a titanium sapphire laser, and used Quantronix company: Integra (Integra). In addition, “PD” means a photo detector, and New Focus (manufactured by New Focus) Co., Ltd .: Cylindrical detector MODEL 818-SL was used. Furthermore, “Amp.” Means an amplifier, manufactured by Stanford RESEARCH SYSTEMS: Low Noise Current Preamplifier (LOW-NOISE CURRENT PREAMPLIFIER) MODEL SR570 and Gated Integrator & Box Car Averager (GATED INTEGRATOR) & BOXCAR AVERAGER) MODEL SR250. “BS” means a beam splitter, and “Quarts cell” means a sample cell made of quartz. Furthermore, “PC” means a personal computer.
測定光源には、フェムト秒チタンサファイアレーザ(波長:800nm、パルス幅:120fs、繰り返し:1kHz、平均出力:2W、強度:2mJ/pulse、ビーム径:10mmφ、ピークパワー:20GW)を用いた。レーザ出力の一部(以下、参照光とする)をBS(ビームスプリッタ)により分岐し、PD(フォトディテクタ)で強度を測定することにより入射光強度の揺らぎを補正した。レーザ出力の残りは、NDフィルタにより10mW程度に減衰させた後、集光レンズにより集光した。この集光されている光路部分に試料溶液を充填した石英セル(光路長:10mm)を置き、その位置を光路に沿って移動させることによりZ−scan測定を実施した。これにより励起光密度を1GW/cm2〜40GW/cm2の範囲で変化させた。 A femtosecond titanium sapphire laser (wavelength: 800 nm, pulse width: 120 fs, repetition rate: 1 kHz, average output: 2 W, intensity: 2 mJ / pulse, beam diameter: 10 mmφ, peak power: 20 GW) was used as a measurement light source. Part of the laser output (hereinafter referred to as reference light) was branched by a BS (beam splitter), and the intensity was measured by a PD (photo detector) to correct fluctuations in incident light intensity. The remainder of the laser output was attenuated to about 10 mW by an ND filter and then condensed by a condenser lens. A quartz cell (optical path length: 10 mm) filled with the sample solution was placed in the condensed optical path portion, and the position was moved along the optical path to perform Z-scan measurement. Thus changing the excitation light density in the range of 1GW / cm 2 ~40GW / cm 2 .
また、試料セルは光路長10mmの石英セルを用いた。試料セルを透過したレーザ光(以下、透過光とする)はNDフィルタにより適当に減衰させ、R72などの色ガラスフィルタを通過させた後、フォトディテクタにより強度を測定した。複数の励起光密度に対してこの測定を実施し、透過光強度を参照光強度で除することにより規格化溶液透過光強度を求めた。 Further, a quartz cell having an optical path length of 10 mm was used as the sample cell. Laser light transmitted through the sample cell (hereinafter referred to as transmitted light) was appropriately attenuated by an ND filter, passed through a colored glass filter such as R72, and the intensity was measured by a photodetector. This measurement was performed for a plurality of excitation light densities, and the normalized solution transmitted light intensity was obtained by dividing the transmitted light intensity by the reference light intensity.
同様の測定配置で試料セルに溶媒のみを充填させ同じ測定を行い、規格化溶媒透過光強度を求めた。さらに、規格化溶液透過光強度を規格化溶媒透過光強度で除することにより透過率を求めた。 In the same measurement arrangement, the sample cell was filled with only the solvent, the same measurement was performed, and the normalized solvent transmitted light intensity was obtained. Further, the transmittance was determined by dividing the normalized solution transmitted light intensity by the normalized solvent transmitted light intensity.
上記のような手順で透過率の励起光密度依存性を測定し、この結果を上記文献に記載されている理論式(i)によりフィッティングし非線形吸収係数を求めた。
Ti=[ln(1+I0L0β)]/I0L0β (i)
(式中、Tiは透過率(%)、I0は励起光密度[GW/cm2]、L0は試料セル長[cm]、βは非線形吸収係数[cm/GW]を示す。)
The dependence of the transmittance on the excitation light density was measured by the procedure as described above, and the result was fitted by the theoretical formula (i) described in the above document to obtain the nonlinear absorption coefficient.
Ti = [ln (1 + I 0 L 0 β)] / I 0 L 0 β (i)
(In the formula, Ti represents transmittance (%), I 0 represents excitation light density [GW / cm 2 ], L 0 represents sample cell length [cm], and β represents nonlinear absorption coefficient [cm / GW].)
この非線形吸収係数から、下記式(ii)により二光子吸収断面積δを求めた。(δの単位は1GM=1×10−50cm4・s・photon−1である。)
δ=1000×hνβ/NAC (ii)
(上記式中、hはプランク定数[J・s]、νは入射レーザ光の振動数[s−1]、NAはアボガドロ数、Cは溶液濃度[mol/L]を示す。)
From this nonlinear absorption coefficient, the two-photon absorption cross section δ was determined by the following equation (ii). (The unit of δ is 1GM = 1 × 10 −50 cm 4 · s · photon −1 .)
δ = 1000 × hνβ / N A C (ii)
(In the formula, h is Planck's constant [J · s], ν is the frequency of the incident laser light [s-1], N A is Avogadro's number, C is concentration of solution [mol / L].)
以上の条件で測定した2光子吸収断面積の評価結果を、表2に示す。また、それぞれの化合物のポルフィリン環同士の二面角をDFT(B3LYP/6−31G)法を用いて計算した結果を表2に併せて示す。以下の表から、本発明における化合物が良好な2光子吸収特性を示すことが明らかである。 Table 2 shows the evaluation results of the two-photon absorption cross section measured under the above conditions. Table 2 also shows the results of calculating the dihedral angle between porphyrin rings of each compound using the DFT (B3LYP / 6-31G) method. From the table below it is clear that the compounds according to the invention show good two-photon absorption properties.
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