Construction of Organic-Inorganic Composite Electron Systems Using Diimine-Platinum Complexes with Pluralitic Interactions

1.二氰基二亚胺铂（II）配合物在玻璃态溶液中的发光性质和组装结构研究在稀的EtOH-MeOH玻璃态溶液中，发现了[Pt（CN）_2（L）]（L= 3，3 ′-联异喹啉（i-biq）和2，2 ′-联吡啶（bpy））的特征发光。对于i-biq复合物，除了单体的^3ππ^* 发射带之外，随着浓度的增加出现宽发射带。宽的谱带是由具有Pt... Pt相互作用的组装物种的^3MLCT态发射的。对于bpy配合物，也观察到类似的发射行为，但宽发射具有准分子特征.（α-二亚胺）（乙二胺）-铂（Ⅱ）和菲型中性π体系的选择性形成堆积物含非平面乙二胺（en），[Pt（en）（L）]^<2+>（L=bpy，phen [1，10-phen]）的配合物选择性地与游离的菲咯啉形成1：1堆积物。π ...更多信息 -π相互作用和氢键使堆叠稳定。发射性质表明，在叠层中，自由菲咯啉向[Pt（en）（L）]^<2+>的能量转移是容易的.具有Pt-Pt链状结构的二氰基（多吡啶）铂（II）配合物表现出对水蒸气和溶剂等环境的特征颜色和发光特性。通过对[Pt（CN）_2（bpy）]的晶体结构的测定，阐明了[Pt（CN）_2（bpy）]的红、黄两种晶型之间的转变机制.含变形π-体系的多吡啶铂（II）配合物的结构和发光性质含芳香族双齿的双（多吡啶）铂（II）配合物被迫变形以避免空间位阻。在这些晶体中发现了两个配体在相反方向上弯曲的弓形构象。在2，2 ′-联喹啉（biq）的配位侧带有扩展的芳环的情况下，合成了高度畸变的配合物[PtCl_2（biq）]。与平面多吡啶配合物相比，具有弓形构象的配合物的发射光谱发生了红移。少

1. Luminescence Properties and Assembled Structures of Dicyano-(diimine) platinum (II) Complexes in Glassy Solution.Characteristic luminescence from the assembled species of [Pt (CN)_2(L)] (L=3,3'-biisoquinoline (i-biq) and 2,2'-bipyridine (bpy)) has been found in a dilute EtOH-MeOH glassy solution. For the i-biq complex, a broad emission band appears with increasing concentration in addition to a ^3ππ^* emission band for the monomer. The broad band is attributable to the emission from the ^3MLCT state of the assembled species with the Pt…Pt interaction. For bpy complex, similar emission behavior is also observed but the broad emission has an excimeric character.2. Selective Formation of the Integrated Stacks of (α-Diimine) (ethylenediamine)-platinum (II) and Neutral π Systems of the Phenanthrene Type.The complexes containing non-planar ethylenediamine (en), [Pt (en)(L)]^<2+> (L=bpy, phen [1,10-phenanthroline]), form a 1 : 1 integrated stack with free phenanthrolines selectively. The π … More -π interactions and the hydrogen bonds stabilize the stack. The emission properties indicate the facile energy transfer from free phenanthrolines to [Pt (en)(L)]^<2+> in the stacks.3. Vapochromism and crystal structures of dicyano (polypyridine) platinum (II)Dicyano (polypyridine) platinum (II) complexes with Pt-Pt linear-chain structure exhibit the characteristic color and luminescence sensing the environment such as vapor and solvents. We have clarified the mechanism of the vapochromism of [Pt (CN)_2(bpy)], the transformation between red and yellow forms, by the determination of the crystal structures of both forms.4. Structures and Emission Properties of Polypyridine Platinum (II) Complexes Containing Deformed π-Systems.Bis (polypyridine) platinum (II) complexes containing aromatic bidentate are forced to deform in order to avoid the steric hindrance. The bow conformation where two ligands warp in the opposite directions has been found for these crystals. In the case of 2,2'-biquinoline (biq) with extended aromatic rings on the side of the coordination site, highly distorted complex, [PtCl_2(biq)] has been synthesized. These complexes having the bow conformation exhibit the red-shifted emission spectra compared with those for complexes with planar polypyridine. Less