Gao Wen-Yang, Tsai Chen-Yen, Wojtas Lukasz, Thiounn Timmy, Lin Chu-Chieh, Ma Shengqian
Department of Chemistry, University of South Florida , 4202 East Fowler Avenue, Tampa, Florida 33620, United States.
Department of Chemistry, National Chung Hsing University , Taichung 402, Taiwan.
Inorg Chem. 2016 Aug 1;55(15):7291-4. doi: 10.1021/acs.inorgchem.6b00937. Epub 2016 Jun 23.
Herein we report a robust primitive cubic (pcu)-topology metal-metalloporphyrin framework (MMPF), MMPF-18, which was constructed from a ubiquitous secondary building unit of a tetranuclear zinc cluster, Zn4(μ4-O)(-COO)6, and a linear organic linker of 5,15-bis(4-carboxyphenyl)porphyrin (H2bcpp). The strong π-π stacking from porphyrins and the lengthy H2bcpp ligand affords a 4-fold-interpenetrating network along with reduced void spaces and confined narrow channels. Thereby, MMPF-18 presents segmented pores and high-density metalloporphyrin centers for selective CO2 uptake over CH4 and size-selective chemical transformation of CO2 with epoxides forming cyclic carbonates under ambient conditions.
在此，我们报道了一种坚固的原始立方（pcu）拓扑结构的金属 - 金属卟啉框架（MMPF），即MMPF - 18，它由常见的四核锌簇二级构筑单元Zn4(μ4 - O)( - COO)6和5,15 - 双（4 - 羧基苯基）卟啉（H2bcpp）的线性有机连接体构建而成。卟啉之间强烈的π - π堆积以及较长的H2bcpp配体形成了一个四重互穿网络，同时减少了空隙空间并限制了狭窄通道。因此，MMPF - 18呈现出分段孔隙和高密度金属卟啉中心，可在环境条件下选择性地吸收CO2而不是CH4，并对CO2与环氧化物进行尺寸选择性化学转化以形成环状碳酸酯。
