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A Chiral Salen-based MOF Catalytic Material with highly thermal, aqueous and chemical stabilities

Abstract

A highly stable chiral salen-based metal-organic framework [(Cu4I4)2L4]•20DMF•3CH3CN (1) [L is (R, R)-N,N’-bis(3-tert-butyl-5-(4-pyridyl)salicylidene)-1,2-diphenylethylenediamine nickel(II)] has been synthesized and characterized by single crystal X-ray diffraction and other physicochemical methods. 1 exhibits a rare 8-fold interpenetrated 3D framework constructed by 4-connecting Cu4I4 cluster and 2-coordinating L ligand. Remarkably, in spite of 8-fold interpenetration, 1 still possesses two types of 1D chiral hydrophobic channels with pore window sizes of 6.77 × 8.64 Å2 and 6.09 × 10.96 Å2 along crystallographic a axis. All Ni(salen) moieties of L lie inside of 1D channels and the empty coordination sites of Ni2+ orient to the cavities. PXRD and N2 adsorption measurements confirmed 1 is extremely stable under high temperature (> 400 oC), in water vapor (90% relative humidity), in acid/base aqueous solution (pH 0-14), and in saturated NaOH solution at 100 oC, as well as in 30 wt% H2O2 and 70 wt% tert-butyl hydroperoxide solution. 1 was proved to be an excellent recycled heterogeneous catalyst for the conversion of simulated industrial CO2 (that is, involving tiny amounts of water vapor and other acidic gas) with epoxides into cyclic carbonates under mild conditions for the first time. The synthesis of β-hydroxy-1,2,3-triazoles from the same epoxides, alkyne and sodium azide was also catalyzed by 1 in aqueous solution with high yield. Interestingly, the cycloaddition reaction of CO2 to bulky epoxides show a decrease in the activity with an increase in the alkyl chain length of the substrate because of confinement of the channel size of 1, showing size-dependent selectivity. The plausible catalytic mechanisms for these two reactions have also been proposed.

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Publication details

The article was received on 28 Mar 2017, accepted on 18 May 2017 and first published on 18 May 2017


Article type: Paper
DOI: 10.1039/C7DT01116D
Citation: Dalton Trans., 2017, Accepted Manuscript
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    A Chiral Salen-based MOF Catalytic Material with highly thermal, aqueous and chemical stabilities

    H. Jiang, L. jiawei, Y. Ren and C. Qi, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT01116D

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