Development and the Mechanistic Study of Luminescent Diimine-Platinum Complexes with Environmental-Sensitivity

环境敏感性发光二亚胺-铂配合物的研制及机理研究

• 批准号: 13640559
• 负责人: KATO Masako
• 金额: $ 2.11万
• 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: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640559/
• 关键词: diimine-platinum complex; vapochromism; crystal structure; luminescent metal complex; bipyridine; emission spectrum; X-ray crystallography; dinuclear platinum complex

(1) Vapochromism and Crystal Structures of Luminescent Dicyano (2,2'-bipyridine) platinum (II). Vapochromic behavior of the title complex has been investigated structurally and emission spectroscopically. The transformation between red and yellow forms is accompanied by the sensitive luminescence change as well as the color change, which reflects the change of the Pt・・・Pt electronic interactions. The sensitive vapochromism for this system is attributable to the slight deformation of the stacking structure induced by water molecules.(2) Dinuclear Bipyridine-platinum (II) Complexes that Exhibit Vapor-Induced Luminescence Switching in Crystals. A new dinuclear platinum (II) complex, syn-[Pt_2 (pyt)_2 (bpy)_2] (PF_6)_2 (pyt = pyridine-2-thiolate ion, bpy = 2,2'-bipyridine), which exhibits a remarkable change in its luminescence sensing organic vapors has been synthesized and characterized. The remarkable properties are investigated on the basis of the structural chemistry and spectroscopies.(3) Development of New Luminescent Platinum Complexes. In order to develop more sophisticated functionality, several new platinum complexes have been synthesized : Modified bipyridine-platinum complexes containing long-alkyl chains, alkylthiol groups, or carboxylic groups have been isolated and characterized. Neutral dinuclear platinum (II) complexes have been obtained by using 2-phenylpyridine instead of bipyridine.(4) Thermal- and Photo-Control of the Linkage Isomerism of Bis (thiocyanato) (2,2'-bipyridine) platinum (II). Three linkage isomers of the title complex were isolated and the structures have been elucidated. The isomerization behaviors among them have been clarified in different media such as solution, crystal, and polymer film.

(1)发光二氰基（2，2 '-联吡啶）铂（II）的蒸气变色和晶体结构通过结构分析和发射光谱研究了标题配合物的汽致变色行为。红色和黄色形式之间的转变伴随着灵敏的发光变化和颜色变化，反映了Pt···Pt电子相互作用的变化。该体系的汽光致变色效应是由于水分子引起的堆积结构的轻微变形所致。(2)双核联吡啶-铂（II）配合物在晶体中表现出蒸气诱导发光转换。合成并表征了一种新的双核铂配合物syn-[Pt_2（pyt）_2（bpy）_2]（PF_6）_2（pyt =吡啶-2-硫醇根离子，bpy = 2，2 ′-联吡啶），该配合物对有机蒸气具有明显的荧光敏感性。在结构化学和光谱学的基础上研究了显着的性质。(3)新型发光铂配合物的研究进展。为了开发更复杂的功能，已经合成了几种新的铂配合物：含有长烷基链、烷基硫醇基或羧基的改性联吡啶-铂配合物已经被分离和表征。用2-苯基吡啶代替联吡啶合成了中性双核铂配合物。(4)双（硫氰基）（2，2 '-联吡啶）铂（II）的键异构性的热和光控制。分离出标题配合物的三个键合异构体，并对其结构进行了鉴定。研究了它们在溶液、晶体和聚合物膜等不同介质中的异构化行为。

项目成果

Shinobu Kishi, Masako Kato: "Vapochromism and crystal structures of Iuminescent dicyano(2,2'-bipyridine)platinum(II)"Molecular Crystals and Liquid Crystals. (in press).

Shinobu Kishi、Masako Kato：“发光二氰基（2,2-联吡啶）铂（II）的气相变色和晶体结构”分子晶体和液晶。

M.Kato and M.Ikemori: "Dichloro (4,4'-dinonyl-2,2'-bipyridine-κ^2N,N') platinum (II)"Acta Crystallogrphica. C59. m25-m26 (2003)

M.Kato 和 M.Ikemori：“二氯 (4,4-二壬基-2,2-联吡啶-κ^2N,N) 铂 (II)”Acta Crystallogrphica (2003)。

Masako Kato: "Vapor-Induced Luminescence Switching in Crystals of the Syn Isomer of a Dinuclear (Bipyridine)platinum(II) Complex bridged with Pvridine-2-thiolate Ions"Angewandte Chemie, International Eiditon. 41. 3183-3185 (2002)

Masako Kato：“与 Pvridine-2-thiolate 离子桥接的双核（联吡啶）铂 (II) 络合物的顺式异构体晶体中的蒸气诱导发光转换”Angewandte Chemie，International Eiditon。

Masako Kato: "Dichloro(4,4'-dinonyl-2,2'-bipyridine-κ^2N,N')platinum(II)"Acta Crystallographica. C59. m25-m26 (2003)

加藤正子：“二氯（4,4-二壬基-2,2-联吡啶-κ^2N,N）铂（II）”晶体学报 C59（2003）。

Masako Kato: "μ-Guanidinido-bis[(terpyridine)platinum(II)] tris(hexafluorophosphate) acetonitrile solvate"Acta Crystallographica. E58. m248-m250 (2002)

加藤正子：“μ-胍基-双[(三联吡啶)铂(II)]三(六氟磷酸盐)乙腈溶剂化物”晶体学报E58(2002)。