The Elucidation of Photophysical and Electronic Properties of Carbazole Chromophore and their Application as a Novel Photo-induced Electron Transfer System

在咔唑烷的帮助下，研究了咔唑（Cz）准分子的结构和形成。咔唑（Cz）准分子的两个Cz环是面对面的，并以不同的几何形状固定。[3]的合成方法。N]（3,9）与烷基链连接的咔唑烷类化合物，在N = 4,5时分别与氰胺或氧桥连接为1n和2n。它们的结构已通过核磁共振和x射线分析得到了明确的表征。揭示了两个Cz环被认为是部分重叠的几何。1n和2n的吸收光谱表明存在跨环π-π电子相互作用。1n和2n的荧光光谱是吸收光谱的镜像，表明它们的荧光是类单体发射。从这些结果来看，1n和2n （n = 4,5）的部分重叠构象结构不足以发射准分子，但可能需要适当的构象，如咔唑环的紧密接触或平行取向。由于报道了Cz与受体对苯二甲酸酯（TP）之间形成外络合物，合成了Cz-对苯二甲酸酯环烷（Cz-TP）。通过核磁共振和x射线分析对Cz-TP的结构进行了表征。随着溶剂介电常数的增加，荧光光谱中发射的峰值波长向更长的波长偏移。在较宽的极性和温度范围内，用Lippert-Mataga关系很好地描述了Cz-TP外杂物发射的极性依赖性。因此，Cz-TP是一种有用的极性探针，可用于评价液相和固相（包括聚合物）的局部极性。还合成了咔唑啉-对苯二甲酸酯三元化合物，其发射行为随着溶剂极性的增加而从准分子变为外展物。结果表明，在men中发生了光致电子转移。

The structure and formation of carbazole (Cz) excimer have been investigated by the help of carbazolopanes, in which two Cz rings are located in face to face orientation and fixed in a distinct geometry.The synthetic methods for [3.n](3,9)carbazolophanes connected with alkylene chain, with cyanamide-or oxa-bridge, 1n and 2n for n = 4, 5, respectively, have been developed. Their structures have been conclusively characterized by ^1H NMR and X-ray analyses. It has been revealed that two Cz rings are taken to be partially overlapped geometry. Absorption spectra of 1n and 2n indicate that the existence of transannular π-π electronic interaction. Fluorescence spectra of 1n and 2n are mirror image of absorption spectra, which show that their fluorescence is monomer-like emission. From these results, the structure of a partially overlapped conformation taken for 1n and 2n (n = 4, 5) is not enough for excimer emission, but may require an appropriate conformation such as close contact or parallel orientation of carbazole rings.As exciplex formation between Cz and acceptor such as terephthalate (TP) was reported, Cz-terephthalate cyclophane (Cz-TP) is synthesized. The structure of Cz-TP has been characterized by NMR and X-ray analysis. The peak wavelengths of the emission in the fluorescence spectra are shifted to a longer wavelength with increases in the dielectric constant of solvents. The polarity dependence of the exciplex emission of Cz-TP is well described by the Lippert-Mataga relation over wide polarity and temperature ranges. Therefore, Cz-TP is a useful polarity probe for the evaluation of local polarity in both liquid and solid phase including polymers.Carbazolophane-terephthalate triads have also synthesized, whose emission behavior change from excimer to exterplex with increases in the polarity of solvents. It has turned out that photoinduced electron transfer has occurred in MeCN.