CN104829636B - 一种黄色磷光三配位阳离子型亚铜配合物发光材料 - Google Patents
一种黄色磷光三配位阳离子型亚铜配合物发光材料 Download PDFInfo
- Publication number
- CN104829636B CN104829636B CN201510277794.0A CN201510277794A CN104829636B CN 104829636 B CN104829636 B CN 104829636B CN 201510277794 A CN201510277794 A CN 201510277794A CN 104829636 B CN104829636 B CN 104829636B
- Authority
- CN
- China
- Prior art keywords
- luminescent material
- tol
- qbi
- yellow
- cuprous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 68
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical compound N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000011368 organic material Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 9
- 238000010668 complexation reaction Methods 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- -1 hexafluoro-phosphate radical Chemical class 0.000 claims description 3
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000000621 Bidens tripartita Nutrition 0.000 claims 1
- 240000004082 Bidens tripartita Species 0.000 claims 1
- 239000013522 chelant Substances 0.000 claims 1
- 208000006637 fused teeth Diseases 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 238000004020 luminiscence type Methods 0.000 abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明公开了一种黄色磷光三配位阳离子型亚铜配合物发光材料及其制备方法。本发明的磷光配合物,由一价铜盐与配体络合得到,其分子结构为Cu(2‑QBI)(o‑Tol3P)(PF6),式中o‑Tol3P和2‑QBI分别为电中性的单齿配体三(邻甲苯基)瞵和双齿配体2‑(2‑苯并咪唑)喹啉。所述配合物既具备小分子易提纯和发光效率高的优点,而且具有易用有机溶剂溶解的优点。该材料是由Cu(CH3CN)4PF6与两种配体的溶液直接分步混合反应得到,具有工艺简便、设备简单、原料易得且成本低等优点。该材料可作为光致发光黄光材料,也可用作多层有机材料组成的电致发光器件中的发光层磷光材料。
Description
技术领域
本发明涉及发光材料技术领域,涉及光致发光材料领域和电致发光材料领域,特别是涉及有机电致发光材料领域。
背景技术
发光材料包括光致发光和电致发光两大类应用领域。光致发光是指物体受到外界光源的照射,从而获得能量产生激发并最终导至发光的现象。紫外辐射、可见光及红外辐射等均可引起光致发光。光致发光材料可用于荧光分析、交通标志、跟踪监测、农用光转换膜、核探测技术中的闪烁体、太阳能转换技术中的荧光集光器等方面。电致发光(electroluminescent,简称EL),是指发光材料在电场作用下,受到电流和电场的激发而发光的现象,是一种将电能直接转换为光能的发光过程。具有这种性能的材料,可制作成电控发光器件,例如发光二极管(LED)和有机发光二极管(Organic Light-Emitting Diode,简称OLED)。而LED和OLED两大类产品,在先进的平板显示和固态节能照明领域都具有非常诱人的应用前景,并且目前已经显示出了其良好的产业化发展势头。
能够产生电致发光的固体材料有很多种,主要包括无机半导体材料、有机小分子材料、高分子材料以及配合物小分子材料。由于OLED具有节能、轻薄、无眩光、无紫外线、无红外线、驱动电压低、响应时间短、低温特性好、发光效率高、制造工艺简单、全固态抗震性好、几乎没有可视角度的问题、能够在不同材质的基板上制造、可做成能弯曲的产品等众多优点,近年来备受科技界和产业界的瞩目。而随着社会的发展,OLED技术已在(或将在)彩电、手机、各种显示器、各种照明用或装饰用灯具、飞机等军事装备的显示终端等领域得到越来越广泛的使用。
OLED器件的工作原理是在外加电场的作用下,空穴和电子分别从正负电极注入器件,在发光层复合形成激子,由激子的辐射衰减发光。而根据自旋统计原理,单重态激子和三重态激子各占25%和75%,所以单纯利用荧光材料制作的发光层,将最多只能利用25%的输入能量,其它大部分能量则会带来严重的发热效应,不仅浪费能源而且不利于器件的长时间稳定工作。与只能利用单重态激子能量的荧光材料不同,过渡金属配合物磷光材料由于具有很强的自旋-轨道耦合作用,可以充分利用包括三重态和三重态的所有输入能量,从根本上突破了很长一段时间内存在的25%能量限制,大幅度提高了OLED器件的效率,也就是说,利用过渡金属配合物磷光材料可以使OLED器件的内部量子效率达到100%。因此在基于OLED器件的发光材料研究中,磷光材料的研发显得尤为重要。
目前OLED产品所采用的磷光体为含铱、铼等贵金属的配合物,它们已经显示了较好的使用性能和市场表现。但是该类贵金属配合物存在成本昂贵,尤其是环境风险的问题。因此,目前针对贱金属Cu(I)配合物磷光材料的研发备受关注,Cu(I)配合物很廉价、无环境风险,因此研究和开发新型的性能优良的Cu(I)配合物发光材料具有重大的意义和很好的市场应用前景。
更具体地进行分析,目前在售的OLED用黄色磷光材料都是贵金属铱和铂等的配合物,虽然它们在性能上已有较好的表现,但是其昂贵的价格也影响到OLED最终产品的推广应用和市场表现。而用Cu(I)配合物作为黄色磷光材料则由来已久(N.Armaroli,G.Accorsi,F.Cardinali,A.Listorti,Top.Curr.Chem.2007,280,69-115.),这种廉价的Cu(I)配合物发光材料可由Cu(I)离子和合适的有机配体方便地制备,只是在OLED工作温度范围其发光强度尚达不到应用需求。因此开发新型廉价的Cu(I)配合物黄色磷光材料具有重大的实际应用价值。
发明内容
本发明的目的是提供一种新的黄色磷光三配位阳离子型亚铜配合物发光材料及其制备方法。通过Cu(I)离子和有机配体的溶液配位反应,方便且廉价地制备获得了发光性能良好的Cu(I)配合物发光材料,其黄色磷光发光强度很大,而且其发光衰减特征非常符合OLED器件对材料磷光发光寿命的要求,将其应用于OLED发光层材料有利于产品成本的降低。
本发明的技术方案之一,是提供一种新的黄色磷光三配位阳离子型亚铜配合物发光材料,由Cu(CH3CN)4PF6与配体进行配位反应得到,其分子结构式为Cu(2-QBI)(o-Tol3P)(PF6),式中o-Tol3P和2-QBI分别为电中性的单齿配体三(邻甲苯基)膦和双齿配体2-(2-苯并咪唑)喹啉。
所述配体2-(2-苯并咪唑)喹啉,是苯并咪唑和喹啉的结合体,其分子结构如式(I):
所述配体中苯并咪唑结构中的一个N和喹啉环中的一个N原子与亚铜离子形成双齿螯合的配位模式。
所述发光材料为三斜晶系,P-1空间群,晶胞参数 α=93.203(4)°,β=105.578(5)°,γ=112.035(5)°,Z=2,Dc=1.475g/cm3,晶体颜色为黄色;该发光材料表现为离子型配合物,其中的抗衡阴离子为六氟磷酸根,而阳离子则是由亚铜离子和配体2-QBI、o-Tol3P络合形成的配位阳离子;该配位阳离子中Cu(I)采用CuN2P平面三角形配位模式,其中两个N分别来自于一个双齿螯合配体2-QBI中的苯并咪唑基团和喹啉基团,而一个P来自于另一个单齿配体o-Tol3P;其分子结构如式(II):
所述发光材料应用于黄光磷光材料,该材料受到很宽波长范围(300-500nm)的紫外光或可见光的激发,都能发出很强的黄色光,其最大发光波长为600nm,色坐标值为(0.5229,0.4709),发光寿命为6微秒。
所述黄色磷光发光材料用作多层有机材料组成的电致发光器件中的发光层磷光材料。
本发明的技术方案之二,是提供一种黄色磷光三配位阳离子型亚铜配合物Cu(2-QBI)(o-Tol3P)(PF6)发光材料的制备方法。该制备方法是由Cu(CH3CN)4PF6和两种配体的在溶液中混合发生配位反应,然后将溶剂除去从而析出产物的晶体而实现。其具体实施方案分为四个步骤:
(1)室温下将Cu(CH3CN)4PF6和o-Tol3P的粉末于二氯甲烷中完全溶解反应;
(2)室温下将配体2-QBI的粉末完全溶解于二氯甲烷中;
(3)将所述两种溶液混合,并搅拌使之充分发生配位反应;
(4)将反应液过滤,并将所得滤液在抽真空条件下旋蒸,除去溶剂即得到黄色的细小晶体产物。
本发明的制备方法中,所述三种反应物的摩尔比Cu(CH3CN)4PF6∶o-Tol3P∶2-QBI为1∶1∶1。
本发明的有益效果首先是所提供的黄色磷光三配位阳离子型亚铜配合物Cu(2-QBI)(o-Tol3P)(PF6)发光材料,其中引入的2-(2-苯并咪唑)喹啉部分有利于分子激发态发光,金属Cu到配体的电荷跃迁(MLCT)的存在有效促进系间窜越,而另一方面大的含取代基的P配体o-Tol3P导致Cu(I)周围存在较大的空间位阻,从而可以稳定亚铜离子的三配位构型,并抑制分子激发态的非辐射衰减,因而该分子材料具有好的磷光发射性能。该配合物材料既具备廉价和易于纯化的优点,而且具有很好的溶解性,为发光材料的进一步应用提供了技术支持。
本发明的有益效果,其次是制备黄色磷光Cu(I)配合物Cu(2-QBI)(o-Tol3P)(PF6)发光材料的方法,具有工艺简便,所用设备简单,原料简单易得,生产成本低,可以在很短的时间内得到具有很高产率的产物等优点。
附图说明
图1.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)分子的单晶结构图。
图2.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)分子在单胞内及其周边空间堆积图。
图3.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)的X-射线粉末衍射图谱:(a)为根据实施例2中单晶结构数据计算获得的谱图;(b)为本发明实施例1中所得粉末的图谱。
图4.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)的傅里叶变换红外(FTIR)光谱图。
图5.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)的紫外-可见吸收(UV-Vis)光谱图。
图6.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)微晶样品在600纳米监控波长下测定的激发谱图。
图7.磷光配合物Cu(2-QBI)(o-Tol3P)(PF6)微晶样品在420纳米波长光激发下的光发射谱图。
具体实施方式
本发明的实现过程和材料的性能由实施例说明:
实施例1
大量的微晶样品的制备:称取112mg Cu(CH3CN)4PF6和74mg的2-QBI配体溶解在10mL二氯甲烷中,称取92mg的o-Tol3P配体溶解在10mL二氯甲烷中(所述三种反应物的摩尔比为1∶1∶1),将这两种溶液混合,并搅拌使之充分发生配位反应,最后将所得黄色溶液过滤,并旋蒸除去所有溶剂,真空干燥,得到黄色晶体粉末即为产物,产率97%(以Cu计)。
实施例2
合成Cu(I)配合物Cu(2-QBI)(o-Tol3P)(PF6)的单晶:称取37mg Cu(CH3CN)4PF6和31mg o-Tol3P配体溶解在10mL二氯甲烷中后,再将25mg的2-QBI配体一次加入上述溶液中,搅拌使之完全溶解后过滤,在滤液上覆盖正己烷促使产物结晶,静置数天后析出大量黄色块状晶体。挑选一颗0.45mm×0.33mm×0.20mm尺寸的黄色晶体用于X-射线单晶结构测试。该化合物的分子结构图示于附图1,其晶胞堆积结构图示于附图2。
对配合物Cu(2-QBI)(o-Tol3P)(PF6)的纯相晶体样品进行了一系列性能测试。对本发明材料晶体进行了稳态荧光测试,结果表明该材料在不同的激发波长作用下,都能发射出强烈的黄光,色坐标值为(0.5229,0.4709),具体的激发光谱和发射光谱如附图6和附图7所示。而对该材料的瞬态荧光测试表明,其发光寿命为6微秒,属于磷光发射。可见,该材料可应用于多种波长激发的黄色磷光材料,也非常适合用于OLED发光层的黄色磷光材料。
Claims (4)
1.一种黄色磷光三配位阳离子型亚铜配合物发光材料,其特征在于:发光材料的结构式为Cu(2-QBI)(o-Tol3P)(PF6),式中o-Tol3P为电中性含P配体三(邻甲苯基)膦;式中2-QBI为电中性杂环配体2-(2-苯并咪唑)喹啉,该配体是苯并咪唑和喹啉的结合体,其分子结构如式(1):
该发光材料为三斜晶系,P-1空间群,晶胞参数α=93.203(4)°,β=105.578(5)°,γ=112.035(5)°,Z=2,Dc=1.475g/cm3,晶体颜色为黄色;该发光材料表现为离子型配合物,其中的抗衡阴离子为六氟磷酸根,而阳离子则是由亚铜离子和配体2-QBI、o-Tol3P络合形成的配位阳离子;该配位阳离子中Cu(I)采用CuN2P平面三角形配位模式,其中两个N分别来自于一个双齿螯合配体2-QBI中的苯并咪唑基团和喹啉基团,而一个P来自于另一个单齿配体o-Tol3P;其分子结构如式(II):
2.根据权利要求1所述黄色磷光三配位型亚铜配合物发光材料的制备方法,该方法包括以下步骤:
(1)室温下将Cu(CH3CN)4PF6和o-Tol3P的粉末于二氯甲烷中完全溶解反应;
(2)室温下将配体2-QBI的粉末完全溶解于二氯甲烷中;
(3)将所述两种溶液混合,并搅拌使之充分发生配位反应;
(4)将反应液过滤,并将所得滤液在抽真空条件下旋蒸,除去溶剂即得到黄色的细小晶体产物;所述三种反应物的摩尔比Cu(CH3CN)4PF6∶o-Tol3P∶2-QBI为1∶1∶1。
3.根据权利要求1所述黄色磷光三配位型亚铜配合物发光材料的应用,其特征在于所述发光材料应用于黄光光致发光材料。
4.根据权利要求1所述黄色磷光三配位型亚铜配合物发光材料的应用,其特征在于所述发光材料用作多层有机材料组成的电致发光器件中的发光层磷光材料。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510277794.0A CN104829636B (zh) | 2015-05-21 | 2015-05-21 | 一种黄色磷光三配位阳离子型亚铜配合物发光材料 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510277794.0A CN104829636B (zh) | 2015-05-21 | 2015-05-21 | 一种黄色磷光三配位阳离子型亚铜配合物发光材料 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104829636A CN104829636A (zh) | 2015-08-12 |
CN104829636B true CN104829636B (zh) | 2017-03-08 |
Family
ID=53807873
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510277794.0A Expired - Fee Related CN104829636B (zh) | 2015-05-21 | 2015-05-21 | 一种黄色磷光三配位阳离子型亚铜配合物发光材料 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104829636B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105713022A (zh) * | 2016-04-18 | 2016-06-29 | 中国计量大学 | 一种苯并咪唑基喹啉亚铜配合物橙色磷光发光材料 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103833777A (zh) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | 一种基于苯并噁唑基喹啉配体的亚铜配合物发光材料 |
-
2015
- 2015-05-21 CN CN201510277794.0A patent/CN104829636B/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103833777A (zh) * | 2014-03-20 | 2014-06-04 | 中国计量学院 | 一种基于苯并噁唑基喹啉配体的亚铜配合物发光材料 |
Non-Patent Citations (1)
Title |
---|
Neutral copper(I) phosphorescent complexes from their ionic counterparts with 2-(2’-quinolyl)benzimidazole and phosphine mixed ligands;Junhui Min, et al.;《Dalton Trans.》;20101202;第40卷;第686-693页 * |
Also Published As
Publication number | Publication date |
---|---|
CN104829636A (zh) | 2015-08-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103588794B (zh) | 一种一价铜配合物发光材料及其制备方法 | |
CN102876320B (zh) | 一种一价铜配合物发光材料及其制备方法 | |
CN104140808B (zh) | 一种含噁唑基吡啶配体的四面体型亚铜配合物发光材料 | |
CN102899029B (zh) | 一种碘化亚铜基配合物发光材料及其制备方法 | |
CN104927842B (zh) | 一种CuIN2P型亚铜配合物红色发光材料 | |
CN104178131B (zh) | 一种含噁唑基吡啶配体的混配型亚铜配合物发光材料 | |
CN104961770B (zh) | 一种基于吡啶基膦配体的亚铜配合物绿色磷光材料 | |
CN104861962B (zh) | 一种基于膦配体的Cu4I4类立方烷簇芯配合物发光材料 | |
CN104893715B (zh) | 一种含有Cu4I4簇芯的碘化亚铜膦配合物发光材料 | |
CN105884829A (zh) | 一种基于苯并噁唑基吡啶的CuIN2P型亚铜配合物发光材料 | |
CN104962281B (zh) | 一种基于苯并噁唑基喹啉的CuN2P2橙色磷光材料 | |
CN104910897B (zh) | 一种Cu3I2阳离子型亚铜簇合物绿色磷光材料 | |
CN102719237B (zh) | 一种Zn(II)配合物发光材料及其制备方法 | |
CN104829636B (zh) | 一种黄色磷光三配位阳离子型亚铜配合物发光材料 | |
CN104892645A (zh) | 一种甲基取代苯并噁唑基吡啶的亚铜配合物磷光材料 | |
CN104861961B (zh) | 一种CuIN2P型四面体配位亚铜配合物发光材料 | |
CN105838356B (zh) | 一种基于苯并噁唑基吡啶的CuBrN2P型亚铜配合物橙色发光材料 | |
CN104830321B (zh) | 一种三配位型双核碘化亚铜配合物发光材料 | |
CN105754590B (zh) | 一种甲基取代苯并噁唑基吡啶亚铜配合物黄色磷光材料 | |
CN105713021A (zh) | 一种甲基取代苯并噁唑基吡啶亚铜配合物黄绿色磷光材料 | |
CN105017336A (zh) | 一种基于二溴取代氮杂芴的CuINP三配位型亚铜配合物发光材料 | |
CN105153230A (zh) | 一种氮杂芴和膦混配的三配位型碘化亚铜配合物发光材料 | |
CN105018071A (zh) | 一种黄绿色磷光的CuIN2P型亚铜配合物发光材料 | |
CN103588798B (zh) | 一种硝酸锌配合物发光材料 | |
CN105017328A (zh) | 一种氮杂芴和单膦配体混配的碘化亚铜配合物发光材料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
EXSB | Decision made by sipo to initiate substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 Termination date: 20180521 |
|
CF01 | Termination of patent right due to non-payment of annual fee |