title: Self-catalysed aerobic oxidization of organic linker in porous crystal for on-demand regulation of sorption behaviours.
abstract: Control over the structure and property of synthetic materials is crucial for practical applications. Here we report a facile, green and controllable solid-gas reaction strategy for on-demand modification of porous coordination polymer. Copper(I) and a methylene-bridged bis-triazolate ligand are combined to construct a porous crystal consisting of both enzyme-like O2-activation site and oxidizable organic substrate. Thermogravimetry, single-crystal X-ray diffraction, electron paramagnetic resonance and infrared spectroscopy showed that the methylene groups can be oxidized by O2/air even at room temperature via formation of the highly active Cu(II)-O2(˙-) intermediate, to form carbonyl groups with enhance rigidity and polarity, without destroying the copper(I) triazolate framework. Since the oxidation degree or reaction progress can be easily monitored by the change of sample weight, gas sorption property of the crystal can be continuously and drastically (up to 4 orders of magnitude) tuned to give very high and even invertible selectivity for CO2, CH4 and C2H6.
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, P. R. China.
authors.forename: Pei-Qin
authors.initials: PQ
authors.lastname: Liao
authors.affiliation: 1] MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, P. R. China [2] Faculty of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650092, P. R. China.
authors.forename: Ai-Xin
authors.initials: AX
authors.lastname: Zhu
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, P. R. China.
authors.forename: Wei-Xiong
authors.initials: WX
authors.lastname: Zhang
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, P. R. China.
authors.forename: Jie-Peng
authors.initials: JP
authors.lastname: Zhang
authors.affiliation: MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, P. R. China.
authors.forename: Xiao-Ming
authors.initials: XM
authors.lastname: Chen