New Aspect for Photophysics and Photochemistry of Coordination Compounds

该项目的主要目的是分享我们在光物理、光化学和光化学分子器件方面的配位化合物的经验和知识。因此，12月20日和21日在东京召开了一场关于配位化合物的光物理和光化学新方面的研讨会。主要讨论了光谱和电子结构、动力学和光致电子和能量转移机理、光化学和光催化剂、配位化合物光化学分子器件的表征等四个方面的内容。结果表明：rac- [Cr(en)_3] -rac- [Cr_xAl_<1-x>(ox)_3]双配合盐在15K时的发光光谱显示出与手性双配合盐相同的振动级数。虽然采用外消旋体[Cr(en)_3]^<3+>作为起始原料，但草酸盐的结构与手性双盐相似。在二氯甲烷-三氯乙酸混合溶剂中，得到了稳定的OTiPc溶液。在将该溶液扩散到水面上形成OTiPc单层膜，并通过水平提升方法沉积在基材上，形成多层膜。从光谱测量的结果来看，很明显分子取向的特定顺序被执行。两亲性卟啉衍生物或其锌络合物也被优先浸渍在超薄聚氯乙烯薄膜的单表面上，这种超薄聚氯乙烯薄膜是通过在水中浇铸分子溶液制备的。获得了薄膜上分子缔合形成的光谱证据。研究了几种新的光催化反应：[Re(bpy)(CO)_3{P(OEt)_3}]^+选择性还原CO_2为CO，[CoH{PPh(OEt)_2}_4]选择性还原烯烃加氢，Sb (V) TPP (OCH_3)_2Br选择性还原环己烯与水的氧化反应。

The main object of this project is to share our experiences and knowledge of coordination compounds in regard to photophysics, photochemistry, and new developments of photochemical molecular devices. Thus a symposium on the new aspect for photophysics and photochemistry of the coordination compounds was open at Dec.20 and 21 in Tokyo. Four subjects were mainly discussed : spectra and electronic structures, dinamics an mechanism of photoinduced electron and energy transfer, photochemistry and photocatalyst, and characterization of photochemical molecular devices of coordination compounds.Following results are obtained : In the double complex salts of rac- [Cr(en)_3] -rac- [Cr_xAl_<1-x>(ox)_3], the luminescence spectrum at 15K shows the same vibronic progression as in chiral double complex salt. The emitting oxalate units have a similar structure to chiral double salt, although racemic [Cr(en)_3]^<3+> was used as a starting material. In dichrolomethane-trichloroacetic acid mixed solvent, a stable solution of OTiPc was obtained. A monolayr of OTiPc was formed upon spreading this solution onto the water surface and was deposited on substrates with a horizontal lifting method to form a multilar film. From the results of spectroscopic measurements, it is clear that a specific order of molecular orientation was performed. An amphiphilic porphyrin derivative or its zinc complex was also preferentially impregnated on a single surface of an ultrathin poly (vinyl chloride) film prepared by casting of molecular solution on water. Spectroscopic evidences for the formation of molecular association on the thin film were obtained. Some new photocatalytic reactions were investigated : [Re(bpy)(CO)_3{P(OEt)_3}]^+for the selective reduction of CO_2 to CO,[CoH{PPh(OEt)_2}_4] for olefin hydrogenations, and Sb (V) TPP (OCH_3)_2Br for oxygenation of cyclohexene with water.