Supramolecular assembly of electrochromic films of terpyridine-functionalized polyiminocarbazolylene metal complexes
Supramolecular assembly of electrochromic films of terpyridine-functionalized polyiminocarbazolylene metal complexes
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三联吡啶功能化聚亚氨基咔唑金属配合物电致变色薄膜的超分子组装
DOI：
10.1039/c0jm03580g
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发表时间：
2011
影响因子：
--
通讯作者：
B. Tieke
中科院分区：
文献类型：
--
作者：
A. Maier;H. Fakhrnabavi;A. R. Rabindranath;B. Tieke
描述了具有三联吡啶取代基的聚亚氨基咔唑啉的制备、金属离子络合和配位组装成有序电致变色薄膜。聚合物 P-2,7 和 P-3,6 通过 Pd 催化 2,7-二溴-N-(2-乙基己基)咔唑或 3,6-二溴-N-(2-乙基己基)咔唑与 4'-(4-氨基苯基)-2,2':6,2"-三联吡啶偶联制备。获得约 3000 Da 的分子量，表明形成了低聚物。该化合物可溶于常见的有机溶剂。 P-3,6 在甲苯、四氢呋喃 (THF) 或二氯甲烷中分别呈现蓝色、绿色或黄色荧光，而 P-2,7 则呈现蓝色荧光，与溶剂的极性无关。发现荧光量子产率高达 68%。添加二价金属盐（例如乙酸锌、乙酸镍或乙酸钴）后，会发生涉及等吸光点的颜色转变。滴定实验表明形成了 2 : 1 和 1 : 1 tpy : 金属离子络合物。如果将预处理的带负电基材（石英、ITO 镀膜玻璃）依次浸入金属六氟磷酸盐的 THF/DMF/正己烷（1 : 0.1 : 1，v/v）溶液和聚合物的 THF/正己烷（1 : 1，v/v）溶液中，则可以制备聚合物-金属离子复合物的有序薄膜。 P-3,6和P-2,7的锌离子和镍离子络合物的膜在中性状态下是黄色的，而含有钴络合物的膜是粉红色的。阳极氧化后，所有薄膜都表现出电致变色特性。含有 P-3,6 的薄膜呈现出绿色和蓝色（锌和镍）或绿棕色（钴）的颜色变化。对于含有 P-2,7 的薄膜，氧化电位通常较高。氧化后，颜色会变成灰色（锌）、橄榄色（镍）或棕色（钴）。即使在环境条件下，所有颜色变化都是可逆的。经过 12 个浸渍循环制备的薄膜的转换时间在 300 ms 至 1.1 s 之间，透光率变化在 800 nm 处较低（2.8% 至 4%），但在 300 nm 处较高（高达 24.6%）。自组装薄膜可用于制备电致变色器件。
Preparation, metal ion complexation and coordinative assembly of polyiminocarbazolylenes with terpyridine substituent groups into organized electrochromic films are described. Polymers P-2,7 and P-3,6 were prepared upon Pd-catalyzed coupling of 2,7-dibromo-N-(2-ethylhexyl)carbazole or 3,6-dibromo-N-(2-ethylhexyl)carbazole and 4′-(4-aminophenyl)-2,2′:6,2″-terpyridine. Molecular weights of about 3 000 Da were obtained indicating the formation of oligomers. The compounds are soluble in common organic solvents. P-3,6 exhibits blue, green or yellow fluorescence in toluene, tetrahydrofuran (THF), or dichloromethane, respectively, whereas P-2,7 exhibits a blue fluorescence independent from the polarity of the solvent. Fluorescence quantum yields up to 68% were found. Upon addition of divalent metal salts such as zinc, nickel or cobalt acetate, colour transitions involving isosbestic points occur. Titration experiments indicate the formation of 2 : 1 and 1 : 1 tpy : metal ion complexes. Organized films of the polymer–metal ion complexes can be prepared, if pretreated negatively charged substrates (quartz, ITO-coated glass) are sequentially dipped into a THF/DMF/n-hexane (1 : 0.1 : 1, v/v) solution of the metal hexafluorophosphates and the THF/n-hexane (1 : 1, v/v) solutions of the polymers. Films of the zinc and nickel ion complexes of P-3,6 and P-2,7 are yellow in the neutral state, whereas films containing the cobalt complex are pink. Upon anodic oxidation, all films exhibit electrochromic properties. Films containing P-3,6 exhibit color changes into green and blue (zinc and nickel) or greenish brown (cobalt). For films containing P-2,7 the oxidation potentials are generally higher. Upon oxidation, color changes into grey (zinc), olive (nickel), or brown (cobalt) are found. All color changes are reversible, even under ambient conditions. Switching times of the films prepared upon twelve dipping cycles are between 300 ms and 1.1 s, the change of transmittance being low (2.8 to 4%) at 800 nm, but rather high at 300 nm (up to 24.6%). The self-assembled films are useful for preparation of electrochromic devices.
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十三核钌(II)-聚吡啶超分子物种：合成、吸收和发光特性以及电化学氧化
影响因子：
4.6
作者：
S. Campagna;G. Denti;S. Serroni;M. Ciano;A. Juris;V. Balzani
通讯作者：
V. Balzani
影响因子：
15
作者：
Louie, J;Hartwig, JF;Fry, AJ
通讯作者：
Fry, AJ
影响因子：
16.6
作者：
Abe, M;Michi, T;Sasaki, Y
通讯作者：
Sasaki, Y
DOI：
10.1016/j.saa.2009.10.015
发表时间：
2010
期刊：
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy
影响因子：
--
作者：
Y. Son;S. Gwon;Sue-Yoen Lee;Sung-Hoon Kim
通讯作者：
Y. Son;S. Gwon;Sue-Yoen Lee;Sung-Hoon Kim
影响因子：
29.4
作者：
Maier, Anna;Rabindranath, Raman;Tieke, Bernd
通讯作者：
Tieke, Bernd