Liu Qiao, Hoefer Nicole, Berkbigler Grant, Cui Zhihao, Liu Tianyu, Co Anne C, McComb David W, Wade Casey R
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Center for Electron Microscopy and Analysis, The Ohio State University, Columbus, Ohio 43210, United States.
Inorg Chem. 2022 Nov 21;61(46):18710-18718. doi: 10.1021/acs.inorgchem.2c03212. Epub 2022 Nov 10.
A novel Zn benzotriazolate metal-organic framework (MOF), [Zn(OAc)(bbtm)] (, bbtm = bis(benzotriazolyl)methanone, OAc = acetate), has been synthesized and structurally characterized using micro-crystal electron diffraction. The framework contains 12-connected nonanuclear Zn clusters with Zn-OAc groups separated by short intercluster Zn···Zn distances of 6.06 Å. Postsynthetic OAc/OH ligand exchange followed by thermal activation generates , which adsorbs CO at very low pressures (1.37 mmol/g at 2.5 mbar) and requires an unusually high desorption temperature (>160 °C). Diffuse reflectance IR Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations have been used to interrogate the CO binding mechanism in . The formation of unsymmetric bridging carbonate ligands within the Zn···Zn pockets accompanied by strong hydrogen bonding of the carbonate with a neighboring zinc aqua ligand explains the remarkably strong CO affinity of .
一种新型的苯并三唑锌金属有机框架（MOF），[Zn(OAc)(bbtm)]（bbtm = 双（苯并三唑基）甲酮，OAc = 乙酸根），已通过微晶电子衍射合成并进行了结构表征。该框架包含12连接的九核锌簇，其中Zn - OAc基团被6.06 Å的短簇间Zn···Zn距离隔开。合成后进行OAc/OH配体交换并随后热活化生成的产物，在非常低的压力下（2.5毫巴时为1.37 mmol/g）吸附CO，并且需要异常高的解吸温度（>160°C）。漫反射红外傅里叶变换光谱（DRIFTS）和密度泛函理论（DFT）计算已用于探究该产物中的CO结合机制。在Zn···Zn口袋内形成不对称桥连碳酸酯配体，同时碳酸酯与相邻的锌水合配体形成强氢键，这解释了该产物对CO具有显著强亲和力的原因。
