Synthesis and 3rd order NLOP roperties of Polycyclic-Dithiines and TTF Derivatives

研究了用于三阶非线性光学材料的新型多环二硫胺和类醌染料的分子设计和合成。这些染料具有大的偶联体系和分子内电荷转移显色体系。在NLO器件中，具有较强的分子内氢键和分子间氢键的染料分子的宽而平的结构对于在晶体或薄膜中产生较强的分子间π - π相互作用非常重要。该体系具有较大的光致极化，有利于制备三阶NLO材料。另一方面，合成了多环二硫胺与TCNQ组成的分子间CT配合物，并对其NLO响应进行了评价。一些类醌染料通过层间pi-pi相互作用在晶体中产生三维分子堆积，这对产生较大的CHI^<(3)>值起重要作用。我们发现了两种新的醌类染料，4,8-二羟基-2,6-二（丁胺）-1,5-萘醌和1,4-二硫酮-3,6-二苯基吡咯[3,4-c]吡咯，它们是三阶NLO材料的候选材料之一。

Molecular design and syntheses of new polycyclic dithiines and quinoid dyes for 3rd order nonlinear optical materials were studied. These dyes have large pi-conjugated systems and intramolecular charge-transfer chromophoric systems. A wide and planar structure of dye molecule with strong intra-and intermolecular hydrogen bonding are very important to produce strong intermolecular pi-pi interactions of dye molecules in crystals or thin film for NLO devices. This system has large photoinduced polarization which is favorable for 3rd order NLO materials.On the other hand, intermolecular CT complexes composed of polycyclic dithiines with TCNQ were also synthesized and their NLO responses were evaluated.Some quinoid dyes produce three dimensional molecular stacking in crystals by interlayr pi-pi interactions which play a great role to produce a large CHI^<(3)> value. We found two types of new quinoid dyes, 4,8-dihydroxy-2,6-bis (butylamino) -1,5-naphthoquinone and 1,4-dithioketo-3,6-diphenylpyrrolo [3,4-c] pyrrole, which were one of the candidates for 3rd order NLO materials.