新型Zn<sup>2+</sup>基金属有机框架结构的温度依赖的导电、发光性能及理论计算

引用本文: 高义粉, 庄桂林, 柏家奇, 钟兴, 王建国. 新型Zn²⁺基金属有机框架结构的温度依赖的导电、发光性能及理论计算[J]. 物理化学学报, 2017, 33(1): 242-248. doi: 10.3866/PKU.WHXB201610103 shu

Citation: GAO Yi-Fen, ZHUANG Gui-Lin, BAI Jia-Qi, ZHONG Xing, WANG Jian-Guo. Temperature-Dependent Conductivity, Luminescence and Theoretical Calculations of a Novel Zn(II)-Based Metal-Organic Framework[J]. Acta Physico-Chimica Sinica, 2017, 33(1): 242-248. doi: 10.3866/PKU.WHXB201610103 shu

新型Zn²⁺基金属有机框架结构的温度依赖的导电、发光性能及理论计算

浙江工业大学化学工程学院, 杭州 310032
基金项目:
国家重点基础研究发展规划项目（973）（2013CB733501）和国家自然科学基金（21176221，21136001，21671172，21306169，91334013）资助

摘要: 通过Zn²⁺和1，3，5-三苯甲酸（H₃BTB）配体反应获得一种新型的四重互穿的金属有机框架结构（MOF）1。单晶体结构分析表明这是一种由中性N，N-二甲基甲酰胺（DMF）分子和H₂NMe₂⁺阳离子沿b轴密封于通道的三维（10，3）网状阴离子框架结构。交流阻抗测试显示该结构的导电性能具有特殊温度依赖性。其电导值在20℃下为0.36×10^-6 S·cm^-1，随着温度升高导电能力迅速增大，160℃达到最大值2.24×10^-5 S·cm^-1，继续升高温度，导电能力开始下降。分子动力学（MD）模拟和介电性质测量表明，这种特殊温度依赖的导电性能是来自于随温度升高H₂NMe₂⁺阳离子迁移增强以及DMF挥发的协同效应。0.20 V的传输能垒接近于质子导电性能。研究表明：MOFs孔对H₂NMe₂⁺的限制作用是获得电子材料的一种潜在理想方法。同时，在1中发现一种有趣的荧光现象，发射峰位置比在H₃BTB配体中更加蓝移。密度泛函理论（DFT）计算揭示这是由于在1中，配体BTB^3-的离域π键结构破坏，禁带宽度增大所致。

关键词:

English

Temperature-Dependent Conductivity, Luminescence and Theoretical Calculations of a Novel Zn(II)-Based Metal-Organic Framework

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P. R. China
Received Date: 01 July 2016
Revised Date: 10 October 2016
Fund Project:
The project was supported by the National Key Basic Research Program of China (973) (2013CB733501) and National Natural Science Foundation of China (21176221, 21136001, 21671172, 21306169, 91334013).

Abstract: Anovel four-fold interpenetrating metal-organic framework (MOF) (1) was obtained following reaction between Zn²⁺ and benzene-1,3,5-tribenzoate (H₃BTB). Single crystal analysis demonstrated that the framework featured a three-dimensional (10, 3) net anionic framework with dimethyl formamide (DMF) and H₂NMe₂⁺ encapsulated in channels along the b axis. Alternating current impedance measurements revealed an unusual temperature-dependent conductance. As the temperature was increased from 20℃ the conductance value increased from 0.36×10^-6 S·cm^-1 to a maximum value of 2.24×10^-5 S·cm^-1 at 160℃, and then began to decrease. A combination of molecular dynamics (MD) simulations and dielectric property measurements demonstrated that this conductance behavior could be attributed to the synergic effect of the enhanced mobility of the H₂NMe₂⁺ cation and removal of DMF as the temperature was increased. Furthermore, the transporting energy barrier was determined to be 0.20 eV, which confirmed that the conductance was caused by proton conductivity. This work indicated that the confinement of H₂NMe₂⁺ within the pores of MOFs is a promising method to induce electrical conductivity. Interestingly, the emission peak of 1 was blue-shifted when compared with that of H₃BTB. Density functional theory (DFT) calculations revealed that this phenomenon was caused by the disruption of delocalized π-bonds within the BTB^3- ligand in 1.

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新型Zn²⁺基金属有机框架结构的温度依赖的导电、发光性能及理论计算

English

Temperature-Dependent Conductivity, Luminescence and Theoretical Calculations of a Novel Zn(II)-Based Metal-Organic Framework

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中国化学会秘书处

新型Zn2+基金属有机框架结构的温度依赖的导电、发光性能及理论计算

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Temperature-Dependent Conductivity, Luminescence and Theoretical Calculations of a Novel Zn(II)-Based Metal-Organic Framework

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