Development of Novel Organic p-Electronic Molecules and Their Application to Color Materials

本研究旨在开发具有三氰基乙烯基团的各种功能材料(如有色材料)，使中性有机π-电子体系之间发生分子间的相互作用。2007年，我们研究了1-芳基-2-(2-噻吩基)-5-(5-三氰基-2-噻吩基)吡咯(1)晶体诱导金属光泽的起源，以及具有TCE基团的新型分子的发展，形成了具有金属光泽的薄膜，取得了以下成果。1)金属光泽来源的理论研究。用平面偏振光研究了π电子分子(1)的排列与金属光泽的关系，阐明了π-分子的连续排列是三氰基乙烯基团与吡咯π-体系分子间相互作用的结果。这一结论也得到了从头算分子轨道方法(B3LYP/6-31G(D))的理论计算支持。2)利用TCE基团开发稳定的金属光泽薄膜去年我们发现，含有两个或两个以上N-[4-(三氰基乙烯基)苯基]苯胺基(TCPA)的化合物形成了具有金属光泽的薄膜。此外，我们一直在研究什么样的含TCPA基团的化合物可以得到稳定的具有金光泽的薄膜。结果表明，3，5-二甲基苯甲酸甲酯的甲基基团为TCPA，苯甲酸甲酯的3-位和5-位基团为TCPA，形成了具有金属光泽的稳定薄膜。此外，还发现苯甲酸酯在3-和5-位上有两个TCPA基团，形成了具有金属光泽的稳定薄膜。

This research aimed the development of various functional materials (for example color material) having tricyanoethenyl (TCE) group, which makes neutral organic π-electronic systems interact with each others intermolecularly. In 2007, we investigated the origin of the metallic luster induced by 1-aryl-2- (2-thienyl) -5- (5-tricyano-2-thienyl) pyrrole (1) crystals as well as the development of novel molecules having TCE groups that form thin film with metallic luster and, as a result, the following fruitful results were gained. 1) Theoretical Investigation of the origin of the metallic luster. The relationship between the arrangement of the π-electronic molecules (1) and the metallic luster were investigated by the use of plane-polarized light that was irradiated on each plane of the single crystal of 1, elucidating that successive arrangement of the π-molecules in such a manner that tricyanoethenyl group interacts with pyrrole π-system intermolecularly. This conclusion was also supported by the theoretical calculation with the ab initio molecular orbital method (B3LYP/6-31G(d)). 2) Development of Stable Metal-lustrous thin films by the Use of TCE Groups Last year, we found that the compounds having two or more N-[4- (tricyanoethenyl) pheny]anilino (TCPA) groups forms a thin film with metallic luster. Furthermore, we have been investigating what kind of compound having TCPA groups can give a stable thin film with gold-like luster. As a result, it was elucidated that methyl 3, 5-dimethylbenzoate having TCPA at the methyl groups and methyl benzoate having TCPA groups at the 3- and 5-positions form a stable thin film with metallic luster. Furthermore, the benzoate ester that has two TCPA groups at 3- and 5-positions was found to form a stable thin film with metallic luster.