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

具有受控纳米结构的发光铂配合物的环境响应特性的开发

• 批准号: 15350034
• 负责人: KATO Masako
• 金额: $ 9.09万
• 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 (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350034/
• 关键词: diimine-platinum complex; vapochromism; crystal structure; luminescent metal complex; substituted bipyridine; emission spectrum; X-ray crystallography; metal-metal interaction

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.

1)含双控取代基的联吡啶铂配合物的环境响应性合成了几种新的含取代联吡啶配体的铂配合物[PtX_2（R_2bpy）]（X=Cl^-，CN^-，R=（CH_2）_nCH_3 [n= 6-10]，COOH），以实现对纳米结构的控制。[Pt（CN）_2（dnbpy）]（dnbpy= 4，4 '-二壬基-2，2'-联吡啶）在固态下表现出气致变色行为，在溶液中表现出灵敏的发光浓度依赖性。X射线衍射分析表明，该配合物通过氢键和Pt-Pt相互作用形成了具有大空腔的三维网状结构。讨论了网络结构的变化与显色性的关系。2）双核联吡啶铂（II）配合物的蒸发变色机理。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）在有机蒸气的作用下，其发光发生了显著的变化。在对配合物结构和光谱研究的基础上，对该配合物的蒸发变色机理进行了初步探讨。这表明，顺式异构体的头对头排列是必不可少的汽致变色行为。

项目成果

Koichi Tanaka: "Guest-dependent Organic Photochromism of 7-Bromo-1,4,7-triphenyl-2,3-benzo[3.3.0]octa-2,4,7-trien-6-one"Journal of Chemical Research (s). 535-537 (2003)

田中浩一：“7-溴-1,4,7-三苯基-2,3-苯并[3.3.0]八-2,4,7-三烯-6-酮的客体依赖性有机光致变色”化学研究杂志

[(1R,2R)-1,2-Diaminocyclohexane-κ^2N, N'](α-diimine-α^2N, N')-platinum(II) bis(hexafluorophosphate), where α-diimine is 2,2'-biphyridine and 1,10-phenanthroline

[(1R,2R)-1,2-二氨基环己烷-κ^2N, N](α-二亚胺-α^2N, N)-铂(II) 双(六氟磷酸盐)，其中 α-二亚胺为 2,2 -联吡啶和1,10-菲咯啉

• 发表时间: 2003
• 期刊: Acta Crystallographica C59
• 作者: T.Koshiyama;M.Kato
• 通讯作者: M.Kato

Shinobu Kishi: "Thermal and Photo control of the Linkage Isomerism of Bis(thiocyanato)(2,2'-bipyridine)platinum(II)"Inorganic Chemistry. 42. 8728-8734 (2003)

Shinobu Kishi：“双(硫氰酸)(2,2-联吡啶)铂(II)联动异构的热和光控制”无机化学。

有機エレクトロルミネッセンス素子

有机电致发光器件

• 发表时间: 2004

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）。