新型Cd-苯并噻二唑类的金属有机骨架中的光诱导脱羧反应

doi:10.7517/j.issn.1674-0475.2017.04.029

影像科学与光化学 ›› 2017, Vol. 35 ›› Issue (5): 686-697.DOI: 10.7517/j.issn.1674-0475.2017.04.029

新型Cd-苯并噻二唑类的金属有机骨架中的光诱导脱羧反应

程清, 余飞虎, 韩晓, 马科, 丁洁, 侯红卫

郑州大学化学与分子工程学院, 河南郑州 450001

收稿日期:2017-05-03 修回日期:2017-05-26 出版日期:2017-09-15 发布日期:2017-09-15
通讯作者: 丁洁, 侯红卫
基金资助:
国家自然科学基金项目（21371155，21301157，21671174）资助

Photoinduced Decarboxylation Reaction in New Cd-benzothiadiazole Metal-organic Framework

CHENG Qing, YU Feihu, HAN Xiao, MA Ke, DING Jie, HOU Hongwei

College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, Henan, P. R. China

Received:2017-05-03 Revised:2017-05-26 Online:2017-09-15 Published:2017-09-15

摘要/Abstract

摘要：

基于相同配体2，1，3-苯并噻二唑-4，7-二羧酸（H₂BTDC），通过不同的溶剂热反应，合成了两个新的3D结构的金属有机框架配合物1[Cd₄（BTDC）₄·5H₂O]和2[Cd₂（BTDC）₂（DMF）·1.5H₂O]。在配合物1的结构中存在两个相邻发色团（BTD单元）为反式平行的排列方式，距离为3.987 Å，小于反式二聚物的理论计算值（4 Å）。在相关的紫外可见吸收光谱中观察到，配合物1在470 nm处吸收带的能量低于单个BTD单元典型吸收带的能量。这些证据揭示了在配合物1的结构中存在反式苯并噻二唑二聚体。通过研究光照前后配合物1和2的稳态光谱及电子顺磁共振（EPR）光谱发现，这两个配合物中存在光诱导电子转移引起的光致变色效应，并产生了相应的阴离子自由基。相关的FT-IR光谱表明，由于这一自由基的产生，配合物1和2进一步发生了配体单元的脱羧反应，释放出二氧化碳气体（2331 cm^-1、2361 cm^-1）。

关键词: 苯并噻二唑-MOF, 光诱导脱羧, 阴离子自由基

Abstract:

Based on the same benzothiadiazole (BTD) ligand (H₂L=2,1,3-benzothiadiazole-4,7-dicarboxylic acid), two new 3D BTD-derived Cd(Ⅱ) metal-organic frameworks 1[Cd₄(BTDC)₄·5H₂O] and 2[Cd₂(BTDC)₂(DMF)·1.5H₂O] were obtained by the different solvothermal reactions. Interestingly, in 1, partial BTD units arranged in an anti-parallel mode, and the distance between these BTD units was 3.987 Å, which was less than that valued by theoretical calculation (4 Å). Furthermore, evidencedby UV-Vis solid state absorption spectra of 1, the energy of absorption band at 470 nm was lower than those from typical monomer-BTD unit. Hence, the structural analysis and photophysical study distinctly demonstrated the evidence of BTD anti-dimmerin 1. More importantly, the UV and fluorescence spectra after illumination showed that there were interesting photochromic phenomena in both complexes 1 and 2 triggered by photoinduced electron transfer, where anionic radical was also directly observed by the electron paramagnetic resonance (EPR) spectra before and after the illumination. Herein, FT-IR spectra show that the subsequent decarboxylation of ligand unit results to release CO₂ gas (2331 cm^-1, 2361 cm^-1) in complexes 1 and 2.

Key words: Benzothiadiazole-MOFs, photo-induced decarboxylation, anionic radical

程清, 余飞虎, 韩晓, 马科, 丁洁, 侯红卫. 新型Cd-苯并噻二唑类的金属有机骨架中的光诱导脱羧反应[J]. 影像科学与光化学, 2017, 35(5): 686-697.

CHENG Qing, YU Feihu, HAN Xiao, MA Ke, DING Jie, HOU Hongwei. Photoinduced Decarboxylation Reaction in New Cd-benzothiadiazole Metal-organic Framework[J]. Imaging Science and Photochemistry, 2017, 35(5): 686-697.

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新型Cd-苯并噻二唑类的金属有机骨架中的光诱导脱羧反应

Photoinduced Decarboxylation Reaction in New Cd-benzothiadiazole Metal-organic Framework

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