新型环状金属Pt(Ⅱ)配合物:合成、晶体结构及光谱性质

doi:10.7517/j.issn.1674-0475.2004.05.370

影像科学与光化学 ›› 2004, Vol. 22 ›› Issue (5): 370-377.DOI: 10.7517/j.issn.1674-0475.2004.05.370

新型环状金属Pt(Ⅱ)配合物:合成、晶体结构及光谱性质

曹迁永¹, 傅文甫^1,2, 贾临芳¹, 于明明¹

1. 中国科学院, 理化技术研究所, 北京, 100101;
2. 云南师范大学, 化学化工学院, 云南, 昆明, 650092

收稿日期:2004-06-25 修回日期:2004-07-01 出版日期:2004-09-23 发布日期:2004-09-23
通讯作者: 傅文甫(1954- ),男,研究员,博士生导师,2001年入选中国科学院百人计划,主要从事光催化、金属有机磷光功能材料的研究,通讯联系人,E-mail:fuwf@mail.ipc.ac.cn.
基金资助:
国家自然科学基金资助项目(50273045;90210033);云南省重点项目(2001E0005Z).

New Cyclometalated Platinum(Ⅱ) Complexes: Synthesis,X-Ray Structure and Electronic Spectra

CAO Qian-yong¹, FU Wen-fu^1,2, JIA Lin-fang¹, YU Ming-ming¹

1. Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100101, P. R. China;
2. College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, Yunnan, P. R. China

Received:2004-06-25 Revised:2004-07-01 Online:2004-09-23 Published:2004-09-23

摘要/Abstract

摘要： 合成了一种新的环状金属配体4-甲氧甲酰基-6-(4-甲基苯基)-2,2’-联吡啶(HL)及它的单核与双核Pt(Ⅱ)配合物[Pt(L)PPh₃](ClO₄)(1)与[Pt₂L₂(μ-dppm)](ClO₄)₂(2)(dppm=二(二苯基磷)-甲烷),并研究了它们的结构及光物理性质.配合物2的晶体结构分析表明,中心金属离子Pt(Ⅱ)呈扭曲平面正方形构型,桥配体dppm连接两个金属中心,0.3375 nm的Pt——Pt距离表明双核配合物中存在金属-金属相互作用.两配合物在～450 nm处的肩峰归属于金属到配体的电荷转移(MLCT)吸收,在固体及溶液中均观测到强烈的光致磷光发射.配合物1在固态时620 nm的低能发射归属为³(π-π)跃迁,并暗示配合物1晶体结构中存在分子间配体-配体相互作用,然而在溶液中仅观察到³MLCT发射光谱,但配合物2在固态及溶液中都观察到明显的金属和金属相互作用到配体的电荷转移(³MMLCT)发射.

关键词: 环金属配体, Pt(Ⅱ)配合物, 晶体结构, 发射光谱

Abstract: A new cyclometalated ligand 4-methoxycarbonyl-6-(4-methylphenyl)-2,2’-bipyridine (HL) and its mono- and binuclear platinum (Ⅱ) complexes (ClO₄) (1) and (ClO₄)₂ (2) (dppm=bis (diphenylphosphino)methane) were synthesized and characterized.In complex 2,the platinum (Ⅱ) center adopts distorted square planar coordination geometry and two platinum (Ⅱ) centers are bridged through biphosphine ligand dppm,and metal-metal interaction exists with Pt-Pt distance 0.3375 nm.Both complexes have low-lying absorption spectra with shoulder peak at ～450 nm which are assigned to metal to ligand charge-transfer transition (MLCT).Both complexes display strong luminescence spectra in solution or solid state.For complex 1,the low energy emission spectra of 620 nm indicates an intermolecular π-π interaction between two ligands in solid state,and in solid or fluid state metal-metal to ligand-charge-transfer (MMLCT) triplet state emissions were observed for complex 2.

Key words: cyclometallated ligand, platinum (Ⅱ) complexes, X-Ray structure, luminescence spectra

中图分类号:

曹迁永, 傅文甫, 贾临芳, 于明明. 新型环状金属Pt(Ⅱ)配合物:合成、晶体结构及光谱性质[J]. 影像科学与光化学, 2004, 22(5): 370-377.

CAO Qian-yong, FU Wen-fu, JIA Lin-fang, YU Ming-ming. New Cyclometalated Platinum(Ⅱ) Complexes: Synthesis,X-Ray Structure and Electronic Spectra[J]. Imaging Science and Photochemistry, 2004, 22(5): 370-377.

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新型环状金属Pt(Ⅱ)配合物:合成、晶体结构及光谱性质

New Cyclometalated Platinum(Ⅱ) Complexes: Synthesis,X-Ray Structure and Electronic Spectra

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