含TEMPO配合物的合成、表征、谱学性质及光猝灭机理

引用本文: 尹璐, 梁程, 陈可先, 赵琛烜, 姚加, 李浩然. 含TEMPO配合物的合成、表征、谱学性质及光猝灭机理[J]. 物理化学学报, 2017, 33(7): 1390-1398. doi: 10.3866/PKU.WHXB201704111 shu

Citation: YIN Lu, LIANG Cheng, CHEN Ke-Xian, ZHAO Chen-Xuan, YAO Jia, Li Hao-Ran. Synthesis, Characterization, Spectroscopic Properties, and Luminescence Quenching Mechanism of a Pt(II) Complex Decorated with a π-Conjugated TEMPO-Terpyridine Ligand System[J]. Acta Physico-Chimica Sinica, 2017, 33(7): 1390-1398. doi: 10.3866/PKU.WHXB201704111 shu

含TEMPO配合物的合成、表征、谱学性质及光猝灭机理

尹璐 ^1, ,
梁程 ^2, ,
陈可先 ^3, ,
赵琛烜 ^1, ,
姚加 ^1, ,
李浩然 ^1,2,

1.
浙江大学化学系, 浙大-新和成联合研发中心, 杭州 310027;
2.
浙江大学化学工程与生物工程学院, 杭州 310027;
3.
浙江工商大学食品与生物工程学院, 杭州 310018
基金项目:
国家自然科学基金（21573196，J1210042），浙江科技创新团队项目（2011R50007），国家高技术研究发展计划项目（863）（SS2015AA020601）和中央高校基本科研业务费专项资金资助

摘要: 通过由2，2，6，6-四甲基哌啶-氮-氧化物（TEMPO）自由基修饰的三联吡啶配体与二价金属铂盐反应，合成得到一种新型的金属配合物，[Pt（terpy-TEMPO）Cl]Cl·H₂O·CH₃OH（terpy指2，2'：6'，2"-三联吡啶）。此配合物由于TEMPO自由基的作用呈现高效率的光猝灭现象。X衍射单晶数据证实此配合物的分子结构信息。利用紫外、荧光及电子顺磁共振光谱等谱学手段探讨了该配合物的紫外吸收、发射及电子顺磁共振（EPR）光谱性质。[Pt（terpy-TEMPO）Cl]Cl·H₂O·CH₃OH的室温紫外吸收光谱表明，此配合物有两个典型的紫外吸收波段，强吸收段和次强吸收段，分别来源于配体到配体的跃迁（MLCT），金属到配体的跃迁（LLCT）。另外，[Pt（terpy-TEMPO）Cl]Cl·H₂O·CH₃OH的室温固体荧光光谱表明，TEMPO的单电子能有效地猝灭三联吡啶铂的荧光发射。我们对此猝灭机理进行了详细合理的阐述，并通过高斯09软件包对配合物的能隙和能带进行了量化计算，结果进一步证明配合物体系中的TEMPO单电子能极大的影响最高占有分子轨道（HOMO）与最低未占分子轨道（LUMO）之间的能级差，从理论上解释了三联吡啶铂配合物的光猝灭的光学性质与分子结构之间的关系。EPR结果表明，稳定自由基上接上金属配合物，不影响自由基A值和g值（A值指自由基超精细耦合常数，g值指自由基的g因子），但影响自由基转动、弛豫时间。

关键词:

English

Synthesis, Characterization, Spectroscopic Properties, and Luminescence Quenching Mechanism of a Pt(II) Complex Decorated with a π-Conjugated TEMPO-Terpyridine Ligand System

1.
ZJU-NHU United R & D Center, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China;
2.
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, P. R. China;
3.
School of Food Science and Biotechnology, Zhejiang Gongshang University Hangzhou, Hangzhou 310018, P. R. China
Received Date: 11 January 2017
Revised Date: 17 March 2017
Available Online: 11 April 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (21573196, J1210042), Program for Zhejiang Leading Team of S&T Innovation (2011R50007), National High Technology Research and Development Program of China (863) (SS2015AA020601), and Fundamental Research Funds of the Central Universities, China.

Abstract: A novel Pt(II)-based metallointercalator terpyridine complex linked with a 2,2,6,6-tetramethyl-1-piperidinyl N-oxide (TEMPO) derivative was prepared by a reaction between 4'-TEMPO-terpyridine (L) and a Pt(II) salt. This complex presented unusual luminescence quenching owing to the effect of the stable nitroxide radical. The crystal structure of[Pt(terpy-TEMPO)Cl]Cl·H₂O·CH₃OH (terpy=2,2':6',2"-terpyridine) was elucidated by X-ray crystallography. Additionally, the effect of TEMPO on the photophysical properties of[Pt(terpy-TEMPO)Cl] Cl·H₂O·CH₃OH was investigated by UV-Vis, fluorescence emission, and electron paramagnetic resonance (EPR) spectroscopy. Data from the absorption and luminescence properties (298 K) of the[Pt(terpy-TEMPO)Cl]⁺ complex indicated the presence of two groups of typical bands:an intense band B with distinct vibronic structures (270-350 nm, ε>10⁴ dm³·mol^-1·cm^-1) and a less intense band A (370-450 nm, ε~10³ dm³·mol^-1·cm^-1). These two bands are generally assigned to ligand-to-ligand charge transfer (LLCT) and metal-to-ligand charge transfer (MLCT) excited states, respectively. Furthermore, efficient photoluminescent quenching behavior was observed in the emission spectra of this complex system. Quantum calculations of the molecular energy gaps and bands were performed by Gaussian 09 software. The calculated results verified that TEMPO greatly affects the energy gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital. Thus, the relationship between efficient photoquenching and molecular structure was theoretically interpreted. EPR results indicated that when TEMPO is attached to a macrocyclic terpyridine platinum complex, e.g.,[Pt(terpy)Cl]⁺, the terpyridine platinum complex does not affect the hyperfine coupling constant (A value) and g factor (g values) but the rotation and relaxation times of the TEMPO radical.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

含TEMPO配合物的合成、表征、谱学性质及光猝灭机理

English

Synthesis, Characterization, Spectroscopic Properties, and Luminescence Quenching Mechanism of a Pt(II) Complex Decorated with a π-Conjugated TEMPO-Terpyridine Ligand System

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

含TEMPO配合物的合成、表征、谱学性质及光猝灭机理

English

Synthesis, Characterization, Spectroscopic Properties, and Luminescence Quenching Mechanism of a Pt(II) Complex Decorated with a π-Conjugated TEMPO-Terpyridine Ligand System

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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