Bicarbazoles: Systematic Structure-Property Investigations on a Series of Conjugated Carbazole Dimers
Bicarbazoles: Systematic Structure-Property Investigations on a Series of Conjugated Carbazole Dimers
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DOI：
10.1021/jo3016538
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发表时间：
2012-10-19
影响因子：
3.6
通讯作者：
Nakamura, Yosuke
中科院分区：
文献类型：
--
作者：
Kato, Shin-ichiro;Noguchi, Hiroto;Nakamura, Yosuke
通过Suzuki-Miyaura， Sonogashira， Hay和McMurry偶联反应合成了一系列共轭咔唑二聚体，即双咔唑1-12。在1-12中，两个咔唑基团直接或通过乙炔或烯烃间隔键连接在1-、2-或3位上。通过广泛的紫外可见光谱和荧光光谱测量、循环伏安法（CV）、理论计算以及x射线晶体图分析，研究了1-12的结构性质关系，特别是共轭连通性和π共轭间隔剂对电子、光物理和电化学性质的影响。咔唑在1位的连接保证了高的偶联度，而在3位的连接增强了给电子能力。乙炔和烯烃的间隔剂都允许扩展偶联，而后者也引起给体能力的增加。此外，发现结构变化对荧光量子产率有显著影响，最高可达0.84。
A large series of conjugated carbazole dimers, namely bicarbazoles 1-12, were synthesized by Suzuki-Miyaura, Sonogashira, Hay, and McMurry coupling reactions. In 1-12, the two carbazole moieties are linked at the 1-, 2-, or 3-position directly or via an acetylenic or olefinic spacer. The structure property relationships, particularly the effects of the conjugation connectivity and the pi-conjugated spacers on the electronic, photophysical, and electrochemical properties of 1-12, were studied by extensive UV-vis and fluorescence spectroscopic measurements, cyclic voltammetry (CV), and theoretical calculations as well as X-ray crystallo-graphic analyses. The connection at the 1-position of carbazole ensures high extent of pi-conjugation, while that at the 3-position enhances the electron donating ability. Both acetylenic and olefinic spacers allow the extension of pi-conjugation, and the latter also causes the increase, of the donor ability. Moreover, the structural variations were found to affect the fluorescence quantum yields significantly, which are up to 0.84.