CN106349259B - 吡啶吡唑铜[i]配合物有机蒸汽发光变色材料及制备方法 - Google Patents
吡啶吡唑铜[i]配合物有机蒸汽发光变色材料及制备方法 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- -1 Pyridine pyrazolate copper Chemical compound 0.000 title claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 20
- 150000003217 pyrazoles Chemical class 0.000 claims abstract description 14
- FSRXIRGQJIHEFB-UHFFFAOYSA-N diphenylphosphane;ethane Chemical compound CC.C=1C=CC=CC=1PC1=CC=CC=C1 FSRXIRGQJIHEFB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910000906 Bronze Inorganic materials 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000010974 bronze Substances 0.000 claims description 5
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- UFITZXXHLWZPNO-UHFFFAOYSA-N perchloric acid;hexahydrate Chemical compound O.O.O.O.O.O.OCl(=O)(=O)=O UFITZXXHLWZPNO-UHFFFAOYSA-N 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 abstract description 9
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 abstract description 6
- QUYPSOKUBYENRV-UHFFFAOYSA-N 1h-pyrazole;pyridine Chemical class C=1C=NNC=1.C1=CC=NC=C1 QUYPSOKUBYENRV-UHFFFAOYSA-N 0.000 abstract description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 150000004699 copper complex Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 208000019901 Anxiety disease Diseases 0.000 description 1
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- RAFKCLFWELPONH-UHFFFAOYSA-N acetonitrile;dichloromethane Chemical compound CC#N.ClCCl RAFKCLFWELPONH-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 238000010537 deprotonation reaction Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- LBLQPCAYBXWESC-UHFFFAOYSA-N pyrazol-1-ide Chemical compound C=1[CH-]C=NN=1 LBLQPCAYBXWESC-UHFFFAOYSA-N 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- C07F1/08—Copper compounds
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- 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
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- C09K9/02—Organic tenebrescent materials
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- C09K2211/1018—Heterocyclic compounds
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Abstract
本发明涉及有机蒸汽发光变色新材料合成技术，特别是一种含吡啶吡唑螯合配体的双核铜[I]配合物有机蒸汽发光变色材料及其制备方法。本发明应用吡啶吡唑螯合配体(5‑三氟甲基‑3‑[2‑吡啶基]吡唑[简称pyfpzH])和有机双膦辅助配体(1,2‑双[二苯基膦]乙烷[简称dppe])，制得一种吡啶吡唑双核铜[I]配合物有机蒸汽发光变色材料[Cu2[pyfpz]2[dppe]2]。常温下该吡啶吡唑双核铜[I]配合物的固态发光波长最大值为493nm，发光寿命为49μs，发光量子效率为71％，而且对二氯甲烷蒸汽表现出快速高效的有机蒸汽发光变色性质。
Description
技术领域
本发明涉及有机蒸汽发光变色新材料合成技术，特别是一种含吡啶吡唑螯合配体的双核铜[I]配合物有机蒸汽发光变色材料及其制备方法。
背景技术
过渡金属发光配合物，因重原子效应和强自旋轨道耦合作用的影响，理论上可利用所有单重态和三重态能量，发光效率可大幅提升。目前，过渡金属发光配合物主要集中于第五、六周期，尤其是第VIII族过渡金属，而钌、锇、铱和铂占据了当前研究的中心位置。第五、六周期的过渡金属元素(除第一、二副族的少数几种金属元素外)在地壳中含量稀少，开采困难，因此基于此类贵金属元素的发光配合物的使用成本较高，而且大规模应用后还会带来原材料来源紧张的问题。另外，此类贵金属元素的配合物通常均有较大毒性，尤其是钌、锇、铼等贵金属配合物，因而，此类贵金属配合物的发光材料在大规模应用后还会带来环境污染及给生产和使用者带来直接或间接伤害。高使用成本及对环境不友好等缺陷使得它们的大规模推广应用受到了极大的限制，因此人们特别期望能在第五、六周期之外寻找到其它可替代的金属元素。
比较第五、六周期的过渡金属元素，位于第四周期的金属铜元素，不仅资源丰富，廉价易得，而且对环境友好，光化学物理性质独特。此外，一价铜配合物还具有优良的室温可见磷光发射，发光可从紫外变到近红外，涵盖整个可见光区。资源丰富、价格低廉、发光性质优良和对环境友好等诸多优点使得一价铜发光配合物在发光器件、光学传感、智能材料、非线性光学材料、光伏器件、光催化等诸多领域表现出良好的应用前景。
目前，在国内外文献中报道的一价铜发光配合物主要集中在一价铜金属簇合物和一价铜单核配合物。一价铜金属簇合物因为结构新颖，几何构型丰富，配位方式多样，光学性质独特等诸多优点，近年来越来越受到人们的极大关注。然而，选用氮杂环多齿螯合配体和有机双膦配体来合成一价铜双核配合物发光变色新材料的文献报道却很少，尤其是一价铜配合物有机蒸汽发光变色材料。
应用吡啶吡唑螯合配体5-三氟甲基-3-[2-吡啶基]吡唑，有机双膦配体为辅助配体，合成一价铜配合物有机蒸汽发光变色新材料的技术，目前尚未见文献公开报道。
发明内容
本发明的目的之一是提供一种吡啶吡唑铜[I]配合物有机蒸汽发光变色材料；
本发明的目的之二是提供一种吡啶吡唑铜[I]配合物有机蒸汽发光变色材料的制备方法。
本发明技术方案：一种吡啶吡唑铜[I]配合物有机蒸汽发光变色材料，即：二[5-三氟甲基-3-[2-吡啶基]吡唑-2-亚基]·二[1,2-双[二苯基膦]乙烷]合二铜[I]配合物，其分子式为：C70H58Cu2F6N6P4，分子结构为：
制备吡啶吡唑铜[I]配合物有机蒸汽发光变色材料的方法之一：
在氩气气氛下，等摩尔比的[Cu[MeCN]4][ClO4]、1,2-双[二苯基膦]乙烷[简称dppe]、5-三氟甲基-3-[2-吡啶基]吡唑[简称pyfpzH]在二氯甲烷中常温搅拌反应2-4小时，之后往该反应液中加入等摩尔量的氢氧化钠，并继续常温搅拌反应1-2小时，然后用旋转蒸发仪将溶剂蒸干，用体积比为1:10的二氯甲烷-石油醚混合溶剂进行重结晶，过滤重结晶得到的淡黄色晶态产物，用乙醚洗涤3-4次，真空干燥后得到淡黄色固体产物——吡啶吡唑铜[I]配合物有机蒸汽发光变色材料。
制备吡啶吡唑铜[I]配合物有机蒸汽发光变色材料的方法之二：
在氩气气氛下，摩尔比为1:5-10:2:2的六水高氯酸铜[Cu[ClO4]2·6H2O]、过量铜粉、1,2-双[二苯基膦]乙烷[简称dppe]、5-三氟甲基-3-[2-吡啶基]吡唑[简称pyfpzH]在体积比为1:2的乙腈-二氯甲烷混合溶剂中常温搅拌反应2-4小时，之后往该反应液中加入与5-三氟甲基-3-[2-吡啶基]吡唑配体等摩尔量的氢氧化钠，并继续常温搅拌反应1-2小时，过滤后用旋转蒸发仪将溶剂蒸干，用体积比为1:10的二氯甲烷-石油醚混合溶剂进行重结晶，过滤重结晶得到的淡黄色晶态产物，用乙醚洗涤3-4次，真空干燥后得到淡黄色固体产物——吡啶吡唑铜[I]配合物有机蒸汽发光变色材料。
本发明采用的反应机理如下：
方法一
方法二：
所得的吡啶吡唑双核铜[I]配合物有机蒸汽发光变色材料的物性参数如下：
分子式：C70H58Cu2F6N6P4；
分子量：1348.2；
中文名称：二[5-三氟甲基-3-[2-吡啶基]吡唑-2-亚基]·二[1,2-双[二苯基膦]乙烷]合二铜[I]配合物；
英文名称：[Cu2[5-trifluoromethyl-3-(2-pyridyl)pyrazol-2-ide]2[1,2-bis(diphenyl phosphino)ethane]2]，简写为：[Cu2[pyfpz]2[dppe]2]。
本发明的发光变色材料在吡啶吡唑螯合配体的吡唑环上引入大空间立体障碍及强拉电子性质的三氟甲基和选用桥联功能的1,2-双[二苯基膦]乙烷，主要用于提高吡啶吡唑螯合配体中吡唑-NH的去质子能力，调节铜[I]配合物的电荷特性、空间立体位阻和电子密度分布，从而有效调控双核铜[I]配合物有机蒸汽发光变色材料的有机蒸汽发光变色性质，在常温下其固体发光波长最大值为493nm，发光寿命为49μs，发光量子效率为71％，而且对二氯甲烷蒸汽表现出快速高效的有机蒸汽发光变色性质。
附图说明
图1为本发明的二[5-三氟甲基-3-[2-吡啶基]吡唑-2-亚基]·二[1,2-双[二苯基膦]乙烷]合二铜[I]配合物晶体结构图。
图2为本发明的二[5-三氟甲基-3-[2-吡啶基]吡唑-2-亚基]·二[1,2-双[二苯基膦]乙烷]合二铜[I]配合物固态荧光发射光谱。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的保护范围。
5-三氟甲基-3-[2-吡啶基]吡唑：根据文献方法自制(S.P.Singh,D.Kumar,B.G.Jones,M.D.Threadgill,J.Fluorine Chem.,1999,94,199-203)。
实施例1：
在氩气气氛下，[Cu[MeCN]4][ClO4](21.6mg，0.066mmol)、1,2-双[二苯基膦]乙烷(26.4mg，0.066mmol)和5-三氟甲基-3-[2-吡啶基]吡唑(14.1mg，0.066mmol)在10mL二氯甲烷中常温搅拌反应3小时，后往该反应液中加入氢氧化钠(2.7mg，0.067mmol)，常温下继续搅拌反应1小时，后用旋转蒸发仪将溶剂蒸干，用二氯甲烷(1mL)-石油醚(10mL)混合溶剂[体积比为1:10]进行重结晶。过滤重结晶得到的淡黄色晶态产物，用10mL乙醚洗涤3-4次，真空干燥后得到淡黄色固体产物——吡啶吡唑铜[I]配合物有机蒸汽发光变色材料(35.1mg，0.026mmol)，产率为79％。
元素分析计算值(C70H58Cu2F6N6P4)为(％)：C 62.36,H 4.34,N 6.23；实测值：C62.39,H4.32,N 6.22.
X-射线单晶衍射：晶体属单斜晶系，P21/c空间群，晶胞参数：a＝21.691(4)，b＝14.919(3)，β＝91.694(4)°，Mr＝1390.64，Z＝4，Dc＝1.409g cm-3，μ＝0.851mm-1，GOF＝1.043，晶体结构如图1所示。
发光性能测试结果表明，该双核铜[I]配合物在常温固态时表现出良好的光致发光性能，最大峰值位于493nm，发光寿命为49μs，发光量子效率为71％，并对二氯甲烷蒸汽表现出快速高效的有机蒸汽发光变色性质，其在二氯甲烷蒸汽气氛和无二氯甲烷蒸汽气氛下的固态荧光发射光谱如图2所示。
实施例2：
在氩气气氛下，六水高氯酸铜[Cu[ClO4]2·6H2O](11.9mg，0.032mmol)和过量铜粉(18.8mg，0.296mmol)在5mL乙腈中常温搅拌反应30分钟，后加入1,2-双[二苯基膦]乙烷(25.6mg，0.064mmol)的10mL二氯甲烷溶液，继续搅拌反应1小时后加入5-三氟甲基-3-[2-吡啶基]吡唑配体(13.7mg，0.064mmol)，常温下继续搅拌反应2小时，后往该反应液中加入氢氧化钠(2.6mg，0.065mmol)，并继续常温搅拌反应1小时，过滤后用旋转蒸发仪将溶剂蒸干，用二氯甲烷(1mL)-石油醚(10mL)混合溶剂[体积比为1:10]进行重结晶。过滤重结晶得到的淡黄色晶态产物，用10mL乙醚洗涤3-4次，真空干燥后得到淡黄色固体产物——吡啶吡唑铜[I]配合物有机蒸汽发光变色材料(32.4mg，0.024mmol)，产率为75％。
分析表征实验数据同实施例1。
Claims (1)
1.一种吡啶吡唑铜[I]配合物作为有机蒸汽发光变色材料的应用，其特征是：所述有机蒸汽为二氯甲烷蒸汽，当所述配合物接触到二氯甲烷蒸汽时能发射一种荧光，
所述的吡啶吡唑铜[I]配合物，即：二[5-三氟甲基-3-[2-吡啶基]吡唑-2-亚基]·二[1,2-双[二苯基膦]乙烷]合二铜[I]配合物，其分子式为：C70H58Cu2F6N6P4，分子结构为：
所述的吡啶吡唑铜[I]配合物的制备方法为下列方法中的一种，方法之一：在氩气气氛下，等摩尔比的[Cu[MeCN]4][ClO4]、1,2-双[二苯基膦]乙烷、5-三氟甲基-3-[2-吡啶基]吡唑在二氯甲烷中常温搅拌反应2-4小时，之后往该反应液中加入等摩尔量的氢氧化钠，并继续常温搅拌反应1-2小时，然后用旋转蒸发仪将溶剂蒸干，用体积比为1:10的二氯甲烷-石油醚混合溶剂进行重结晶，过滤重结晶得到的淡黄色晶态产物，用乙醚洗涤3-4次，真空干燥后得到淡黄色固体产物——吡啶吡唑铜[I]配合物；
方法之二：在氩气气氛下，摩尔比为1:5-10:2:2的六水高氯酸铜[Cu[ClO4]2·6H2O]、过量铜粉、1,2-双[二苯基膦]乙烷、5-三氟甲基-3-[2-吡啶基]吡唑在体积比为1:2的乙腈-二氯甲烷混合溶剂中常温搅拌反应2-4小时，之后往该反应液中加入与5-三氟甲基-3-[2-吡啶基]吡唑配体等摩尔量的氢氧化钠，并继续常温搅拌反应1-2小时，过滤后用旋转蒸发仪将溶剂蒸干，用体积比为1:10的二氯甲烷-石油醚混合溶剂进行重结晶，过滤重结晶得到的淡黄色晶态产物，用乙醚洗涤3-4次，真空干燥后得到淡黄色固体产物——吡啶吡唑铜[I]配合物。
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