Development of Energy Conversion Systems by Use of Inorganic/Organic Hybrid LB Films

这项工作试图阐明一种具有新功能的光响应界面。研究了以下三个方面的内容：(1)制备单层剥离粘土修饰电极；(2)利用光响应性金属络合物作为手性掺杂剂来控制胆甾型液晶相的结构；(3)利用粘土-金属络合物作为吸附剂实现不对称合成。对于(1)，Δ-[Os(Phen)_3]~(2+)&lt；2+&gt；/粘土修饰电极能够在电化学上识别1，1‘-联苯酚的对映体。利用两亲性铂(II)络合物的LB膜修饰电极(与北海道大学的M.Kato教授合作)将光子能量转换为电性能量。对于(2)，合成了含偶氮苯基团的三(β-二酮)Ru(III)络合物，并将其作为手性掺杂剂诱导手性向列相。在紫外光和可见光照射下，络合物的顺反异构化导致螺旋螺节长度发生可逆变化。至于(3)，硫化物的光氧化反应是通过吸附在Δ-[Ru(Bpy)_3]^&lt；2+/粘土的离子交换加合物上进行的。这是一个罕见的多相不对称反应的例子。

This work attempted to elucidate a photoresponsive interface with novel functions. The following three topics were studied: (1) To develop an electrode modified with a single layer of exfoliated clay sheets; (2) To control the structure of cholesteric liquid crystal phases by use of photoresponsive metal complexes as a chiral dopant; (3) To achieve asymmetric syntheses by use of clay-metal complex as an adsorbent.As for (1), an electrode modified with a LB film of Δ-[Os(phen)_3]^<2+>/clay was able to discriminate enantiomers of 1,1'-binaphthol electrochemically. An electrode modified with a LB film of amphiphilic Pt(II) complex was used to convert photon energy to electric one (collaboration with Prof.M.Kato (Hokkaido University)).As for (2), tris(β-diketonato)Ru(III) complex with azobenzene moiety was synthesized and used as a chiral dopant to induce chiral nematic phases. The cis-trans isomerization of the complex resulted in the reversible change of helical pitch length under the illumination of UV and visible lights.As for (3), the photo-oxidation reaction of sulfide was performed by being adsorbed on an ion-exchange adduct of Δ-[Ru(bpy)_3]^<2+>/clay. This was a rare example of heterogeneous asymmetric reactions.