CN101891895A - 基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物及其制法及应用 - Google Patents
基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物及其制法及应用 Download PDFInfo
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- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 8
- 239000013256 coordination polymer Substances 0.000 title abstract description 7
- 229920001795 coordination polymer Polymers 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 19
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical group OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 10
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 2
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 239000004305 biphenyl Substances 0.000 abstract 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 150000001875 compounds Chemical group 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- -1 benzothiazole compound Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012356 Product development Methods 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002772 conduction electron Substances 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
技术领域
本发明涉及金属有机配位聚合物及其合成方法和应用,具体地说是基于桥联双水杨醛结构的苯并噻唑类配体的合成、金属配位聚合物的合成,及其在有机电致发光材料方面的应用。
背景技术
对于产品:文献上尚无报导,所合成的是一种基于桥联双水杨醛结构的新型的金属有机配位聚合物。
对于方法:简单的苯并噻唑类化合物的合成一般在DMSO中进行,同类的配合物一般在醇溶液中进行。
对于应用:所合成的基于双水杨醛结构的苯并噻唑类配位聚合物是一种新的配合物,还没有以它作为有机电致发光材料方面应用的报道。
由于现有显示技术无法满足人们对信息显示设备越来越高的要求,有机电致发光器件(organic light-emitting device,OLED)作为新一代的平板显示技术应运而生并逐渐进入了人们的视野,它是一种很有前途的、新型的平板显示器(flat panel display,FPD),其广泛的应用前景和这些年技术上的突飞猛进使得OLED成为FPD信息显示领域和科学研究产品开发最热门的话题之一。从有机EL器件的结构来考虑,用于有机EL器件的材料可以分为:电极材料、载流子传输材料和发光材料。而发光材料在EL器件中使最重要的材料。选择发光材料必须满足下列要求:
1.高量子效率的荧光特性,且荧光光谱主要分布在400~700nm可见光区域内;
2.良好的半导体特性,即具有高的导电率或能传导电子、或者能传导空穴、或两者兼有;
3.良好的成膜性,在几十个纳米的薄层中不产生针孔;
4.良好的热稳定性。
目前为止,人们已对大量的有机化合物作为发光材料进行了研究。按化合物结构可以最一般的分为两大类:小分子有机化合物和高分子聚合物。由于小分子的玻璃化转变温度低,器件工作时产生的焦耳热易使小分子材料重结晶而无法制备长寿命的器件;高分子发光材料由于分子量大的原因,化合物难以提纯,而且必须通过引入供/吸电基团来提高电子/空穴平衡注入/传输能力,引入大体积基团或者形成非共平面的扭曲结构以减少链间聚集,减少荧光淬灭,提高量子效率以及提高稳定性等。近年来,人们发展了一系列结合两者特点的高分子主链接枝型、主链官能化配位型和端基配位型聚合物。金属离子在共轭聚合物中的引入带来了一系列新的特点,如颜色可调、电荷移动性改善、发光效率高等等([1]黄春辉,李富友等.光电功能超薄膜[M].北京:北京大学出版社,2001)。
发明内容
发明目的:本发明的目的是提供一类基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物及其制法及应用。该苯并噻唑类金属配位聚合物具有良好的热稳定性、好的荧光发射性能,制备方法简单,该类型的配位聚合物可以在有机电致发光材料方面得到应用。
技术方案:基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物,具有以下结构:
其中linker=CH2或C(CH3)2
R=H+、卤素基、苯基或联苯基;
M=Zn2+,Be2+或Ca2+。
制备基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物的方法,制备步骤为:
a.将双芳醛与氨基苯硫酚按摩尔配比1∶2.1混合后,在DMSO中回流反应3小时;
b.反应结束后,倒入水中,饱和食盐水破乳,CH2Cl2萃取后合并有机相得粗产品;
c.粗产品以硅胶柱层析分离提纯得到配体;
d.将配体与Zn2+,Be2+或Ca2+金属盐按摩尔配比1∶1.1混合,室温下搅拌反应24小时;反应中加入Et3N促进反应;
e.反应结束后,离心分离,洗涤、干燥后得到基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物。
上述步骤d中配体溶解在二氯甲烷中,金属盐溶解在乙醇中,两种溶剂的体积比1∶1。
基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物在有机电致发光材料中的应用。
有益效果:本发明与现有技术相比,具有以下显著优点:
(1)本发明的基于双水杨醛结构的苯并噻唑类配体合成方法简单,产率适中。
(2)本发明的基于双水杨醛结构的苯并噻唑类金属有机配位聚合物具有好的热稳定性,分解温度大于500℃,强的荧光发射和合适的发光波长。
(3)本发明中不同的桥联结构以及柔性基团的引入可以显著改善了聚合物的溶解性,调节发光波长,可以在有机电致发光材料发面得到应用。
(4)本发明的基于双水杨醛结构的苯并噻唑类配体的发光波长在540nm~580nm之间,配合物的发光波长在470~490nm之间。
(5)合成方法简便,工艺操作简单,产率高,成本低。
具体实施方式
实施例1.
在封管中加入醛128mg(0.5mmol),氨基苯硫酚131mg(1.05mmol,2.1eq),DMSO2.5mL,185℃反应3h。反应液冷却至室温后倒入60mL水中即出现白色乳液,加入5mL饱和食盐水破乳,CH2Cl2萃取(15mL×3)。合并有机相,干燥浓缩后柱层析(石油醚/乙酸乙酯=20∶1),得到淡黄色固体,即为配体,产率为36%。1H NMR(CDCl3,300MHz,ppm)δ:12.45(s,2H),7.99(d,J=8.1Hz,2H),7.89(d,J=7.8Hz,2H),7.53~7.48(m,4H),7.41(t,J=7.5Hz,2H),7.24(d,J=8.4Hz,2H),7.07(d,J=8.4Hz,2H),4.01(s,2H).13C NMR(CDCl3,300MHz,ppm)δ:169.4,156.6,152.0,133.6,132.7,132.0,128.4,126.8,125.7,122.3,121.7,118.3,116.8,40.0.
IR(KBr压片)cm-1:v 3058,2839,1625,1591,1498,1438,1266,1216,996,760.
实施例2.
向溶有0.05mmol(23.3mg)的配体的二氯甲烷溶液中,滴加溶有0.055mmol(1.1eq,7mg)Zn(OAc)2·2H2O的乙醇溶液2mL,再加入0.1mmol(2eq,14μL)三乙胺,室温搅拌反应24h。反应结束后离心分离(5000rpm,2min)。乙醇、乙醚依次洗涤即得到目标化合物,干燥后称重,产率:78%。IR(KBr压片)cm-1:v 3059,1617,1589,1536,1497,1446,1397,1342,1215,998,825,756.
实施例3.
在封管中加入醛142mg(0.5mmol),氨基苯硫酚131mg(1.05mmol,2.1eq),DMSO 2.5mL,185℃反应3h。反应液冷却至室温后倒入60mL水中即出现白色乳液,加入5mL饱和食盐水破乳,CH2Cl2萃取(15mL×3)。合并有机相,干燥浓缩后柱层析(石油醚/乙酸乙酯=20∶1),得到淡黄色固体,即为配体,产率为46%。1H NMR(CDCl3,300MHz,ppm)δ:12.45(s,2H),8.01(d,J=8.1Hz,2H),7.89(d,J=8.1Hz,2H),7.64(d,J=8.1Hz,2H),7.52(t,J=7.4Hz,2H),7.41(t,J=7.7Hz,2H),7.30(dd,J=2.1,10.8Hz,2H),7.07(d,J=8.7Hz,2H),1.81(s,6H).13C NMR(CDCl3,300MHz,ppm)δ:169.7,156.2,152.1,141.6,132.2,126.8,125.9,125.6,122.3,122.2,121.6,117.9,116.1,41.9,31.0.IR(KBr压片)cm-1:v 3448,3052,2967,1625,1594,1499,1232,1207,1191,989,830,752.
实施例4.
向溶有0.05mmol(24.7mg)的配体的二氯甲烷溶液中,滴加溶有0.055mmol(1.1eq,7mg)Zn(OAc)2·2H2O的乙醇溶液2mL,再加入0.1mmol(2eq,14μL)三乙胺,室温搅拌反应24h。反应结束后离心分离(5000rpm,2min)。乙醇、乙醚依次洗涤,干燥后称重。产率:88%。IR(KBr压片)cm-1:v 3059,2964,1612,1530,1494,1447,1393,1192,1157,989,832.
实施例5.
在封管中加入醛218mg(0.5mmol),氨基苯硫酚131mg(1.05mmol,2.1eq),DMSO2.5mL,185℃反应3h。反应液冷却至室温后倒入60mL水中即出现白色乳液,加入5mL饱和食盐水破乳,CH2Cl2萃取(15mL×3)。合并有机相,干燥浓缩后柱层析(石油醚/乙酸乙酯=20∶1),得到淡黄色固体,即为配体,产率为66%。1H NMR(CDCl3,300MHz,ppm)δ:13.04(s,2H),7.92(d,J=8.1Hz,2H),7.86(d,J=7.8Hz,2H),7.66~7.61(m,3H),7.50~7.32(m,6H),1.84(s,6H).13C NMR(CDCl3,300MHz,ppm)δ:170.0,153.6,151.9,141.4,138.1,133.2,132.8,130.7,129.6,128.3,127.5,126.8,125.7,125.4,122.2,121.6,116.4,42.2,31.2.IR(KBr压片)cm-1:v 3431,3056,2962,2928,2861,1612,1496,1461,1430,1241,757.
实施例6.
向溶有0.05mmol(32.3mg)的配体的二氯甲烷溶液中,滴加溶有0.055mmol(1.1eq,7mg)Zn(OAc)2·2H2O的乙醇溶液2mL,再加入0.1mmol(2eq,14μL)三乙胺,室温搅拌反应24h。反应结束后离心分离(5000rpm,2min)。乙醇、乙醚依次洗涤,干燥后称重。产率:76%.IR(KBr压片)cm-1:v 3057,2962,1603,1541,1485,1447,1421,1322,1238,757.
实施例7.
在封管中加入醛294mg(0.5mmol),氨基苯硫酚131mg(1.05mmol,2.1eq),DMSO2.5mL,185℃反应3h。反应液冷却至室温后倒入60mL水中即出现白色乳液,加入5mL饱和食盐水破乳,CH2Cl2萃取(15mL×3)。合并有机相,干燥浓缩后柱层析(石油醚/乙酸乙酯=20∶1),得到淡黄色固体,即为配体,产率为67%。1H NMR(CDCl3,300MHz,ppm)δ:13.11(s,2H),7.95(d,J=8.1Hz,2H),7.88d,J=7.8Hz),7.74~7.62(m,8H),7.52~7.34(m,5H),1.87(s,6H).13C NMR(CDCl3,300MHz,ppm)δ:170.0,153.7,151.9,141.5,141.1,140.4,137.1,133.1,132.8,130.8,130.0,128.9,127.4,127.3,127.1,126.9,125.5,122.3,121.67,42.3,31.2,29.9.IR(KBr压片)cm-1:v 3056,3028,2963,2925,2850,1613,1494,1440,1247,1122,841,758,727.
实施例8.
向溶有0.05mmol(40.0mg)的噻唑的二氯甲烷溶液中,滴加溶有0.055mmol(1.1eq,7mg)Zn(OAc)2·2H2O的乙醇溶液2mL,再加入0.1mmol(2eq,14μL)三乙胺,室温搅拌反应24h。反应结束后离心分离(5000rpm,2min)。乙醇、乙醚依次洗涤,干燥后称重。产率:80%。IR(KBr压片)cm-1:v 3063,3027,2964,1604,1539,1485,1447,1398,1238,1009,758.
实施例9.
分别对实施例1~8中合成的配位聚合物,采用Cary Eclipse荧光光度计(美国Varian公司),以1×10-5mol/L的CH2Cl2溶液中测试荧光,配体和配合物都有强的荧光发射,配体的发光峰均位于540nm~580nm之间,属于绿光范围之内,各种配位聚合物的发光峰波长位于470~490nm之间,属于蓝绿光区域。对配合物进行TG/DTA表征,测试在氮气氛下进行,升温速度20℃/min。结果表明配合物的分解温度在500℃以上。
Claims (4)
1.基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物,其特征在于具有以下结构:
其中linker=CH2或C(CH3)2
R=H+、卤素基、苯基或联苯基;
M=Zn2+,Be2+或Ca2+。
2.制备基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物的方法,其特征在于制备步骤为:
a.将双芳醛与氨基苯硫酚按摩尔配比1∶2.1混合后,在DMSO中回流反应3小时;
b.反应结束后,倒入水中,饱和食盐水破乳,CH2Cl2萃取后合并有机相得粗产品;
c.粗产品以硅胶柱层析分离提纯得到配体;
d.将配体与Zn2+,Be2+或Ca2+金属盐按摩尔配比1∶1.1混合,室温下搅拌反应24小时;反应中加入Et3N促进反应;
e.反应结束后,离心分离,洗涤、干燥后得到基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物。
3.根据权利要求2所述的制备基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物的方法,其特征在于步骤d中配体溶解在二氯甲烷中,金属盐溶解在乙醇中,两种溶剂的体积比1∶1。
4.基于桥联双水杨醛结构的苯并噻唑类金属配位聚合物在有机电致发光材料中的应用。
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