Development of Environment Responsive Properties of Luminescent Platinum Complexes Having Controlled Nano Structures

1)含排位控制取代基的（联吡啶）铂配合物的环境响应特性。为了精细控制纳米结构，合成了几种含取代联吡啶配体[PtX_2(R_2bpy)] （X=Cl^-, CN^-， R=(CH_2)_nCH_3 [n= 6-10]， COOH）的新型铂配合物。[Pt(CN)_2(dnbpy)] （dnbpy=4,4′-二酰-2,2′-联吡啶）在固相中表现出气相变色行为，在溶液中对发光具有敏感的浓度依赖性。对于含有羧基的配合物，发现了ph依赖的显色现象。x射线分析表明，具有大空腔的三维网络结构是由氢键和Pt-Pt相互作用构成的。讨论了网络结构变化与显色性的关系。2)双核联吡啶-铂（ll）配合物的气相变色行为机理。双核铂（II）配合物syn-[Pt_2(pyt)_2(bpy)_2](PF_6)_2 （pyt=吡啶-2-硫酸盐离子，bpy=2,2′-联吡啶）在感应有机蒸汽时表现出显著的发光变化。在相关配合物的结构和光谱研究的基础上，进行了气相变色的机理研究。结果表明，同分异构体的头对头排列对气相变色行为至关重要。

1) Environment Responsive Properties of (Bipyridine)platinum(II) Complexes Containing Arrangement-controlling Substituents. Several new platinum complexes containing substituted bipyridine ligands, [PtX_2(R_2bpy)] (X=Cl^-, CN^-, R=(CH_2)_nCH_3 [n= 6-10], COOH) have been synthesized in order to control nano-structures sophisticatedly. [Pt(CN)_2(dnbpy)] (dnbpy=4,4'-dinonyl-2,2'-bipyridine) exhibited vapochromic behavior in the solid states and sensitive concentration dependence of luminescence in solution. For the complex containing carboxyl groups, pH-dependent chromism was found. The X-ray analysis revealed that three-dimensional network structure having large cavities was constructed with hydrogen bonds and Pt-Pt interactions. The relationship between the network structural change and the chromism was discussed.2) The Mechanism of the Vapochromic Behavior of a Dinuclear Bipyridine-platinum(ll) Complex. The dinuclear platinum(II) complex, syn-[Pt_2(pyt)_2(bpy)_2](PF_6)_2 (pyt=pyridine-2-thiolate ion, bpy=2,2'-bipyridine) exhibits a remarkable change in its luminescence by sensing organic vapors. Mechanistic studies of the vapochromism have been carried out on the basis of the structural and spectroscopic investigations of related complexes. It is suggested that the head-to-head arrangement of the syn isomer is essential to the vapochromic behavior.