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

利用具有多元相互作用的二亚胺-铂配合物构建有机-无机复合电子体系

• 批准号: 11640566
• 负责人: KATO Masako
• 金额: $ 2.18万
• 依托单位: Nara Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640566/
• 关键词: diimine-platinum compelx; stacking structure; π-π interaction; metal-metal interaction; luminescent complex; highly distorted complex; selective assembladge; vapochromism; 分子間相互作用; 積層構造; 有機-無機複合系; 複合結晶; 発光特性; 選別集積機能; π-スタック

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

1. 玻璃溶液中二氨基-（二亚胺）铂（II）配合物的发光性质和组装结构。[Pt (CN)_2(L)] （L=3,3′-生物异喹啉（i-biq）和2,2′-联吡啶（bpy））组装物在稀乙炔-甲醇玻璃溶液中发现了特征性发光。对于i-biq配合物，除了单体的^3ππ^*发射带外，随浓度的增加还出现了较宽的发射带。宽带是由于与Pt…Pt相互作用的组合体的^3MLCT态发射所致。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体系的选择性形成含有非平面乙二胺（en）， [Pt (en)(L)]^<2+> （L=bpy, phen[1,10-菲罗啉]）的配合物选择性地与游离菲罗啉形成1:1的积层。π…更多的-π相互作用和氢键稳定了堆叠。发射特性表明，能量从游离菲罗啉转移到[Pt (en)(L)]^<2+>。具有Pt-Pt线性链结构的双氰（多吡啶）铂（II）配合物的气相变色和晶体结构表现出对蒸汽和溶剂等环境敏感的特有颜色和发光特性。通过对[Pt (CN)_2(bpy)]和[Pt (CN)_2(bpy)]两种形式的晶体结构的测定，阐明了两种形式的气相变色机理和红、黄两种形式的转变。含变形π系的多吡啶铂（II）配合物的结构与发射性能。含芳香双齿的双（多吡啶）铂（II）配合物被强制变形以避免位阻。在这些晶体中发现了两个配体向相反方向弯曲的弓形构象。以2,2′-联喹啉（biq）为例，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表现出红移的发射光谱。少

项目成果

Masako Kato: "Two-Dimensional Stacking of Dichloro(dipyridophenazine)platinum(II)"Acta Crystallographica. C55. 1809-1812 (1999)

加藤正子：“二氯（二吡啶吩嗪）铂（II）的二维堆积”晶体学报。

T.Funayama, M.Kato, H.Kosugi, M.Yagi, J.Higuchi, and S.Yamauchi: "Studies of the Lowest Excited Triplet State of [Pt(i-biq) (CN)_2] by means of Time-Resolved EPR and Optical Spectroscopy"Bulletin of the Chemical Society of Japan. 73. 1541-1550 (2000)

T.Funayama、M.Kato、H.Kosugi、M.Yagi、J.Higuchi 和 S.Yamauchi：“通过时间研究 [Pt(i-biq) (CN)_2] 的最低激发三重态

Masako Kato: "Anion-Controlled π-Stack ccf (Ethylenediamine-N, N')(1, 10-phenanthroline-N, N')-platinum(II)"Acta Crystallographica. C55. 1809-1812 (1999)

Masako Kato：“阴离子控制 π-Stack ccf（乙二胺-N，N）（1, 10-菲咯啉-N，N）-铂（II）”晶体学报 C55（1999）。

M.Kato and J.Takahashi: "Anion-Controlled π-Stack of (Ethylenediamine-N,N') (1,10-phenanthroline-N,N') platinum (II)"Acta Crystallographica.. C55. 1809-1812 (1999)

M.Kato 和 J.Takahashi：“(乙二胺-N,N) (1,10-菲咯啉-N,N) 铂的阴离子控制 π 堆栈 (II)”晶体学报.. C55。 (1999)

Masako Kato: "Selective formation of the integrated stacks of (α-diimine) (ethylenediamine)-platinum (II) and neutral π systems of the phenanthrene type"Journal of the Chemical Society, Dalton Transactions. 747-752 (2001)

Masako Kato：“选择性形成 (α-二亚胺) (乙二胺)-铂 (II) 和菲型中性 π 系统的集成堆栈”，《化学学会杂志》，Dalton Transactions 747-752 (2001)。