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Thiophene insertion for continuously modulating photoelectronic property of triphenylamine-based metal-organic framework for photocatalytic sulfonylation-cyclisation of activated alkenes

Abstract

The pharmaceutically meaningful conversions like photocatalytic sulfonylation calls for the precise control of photoelectronic property of photocatalyst. A ligand engineering strategy by inserting different numbers of thiophenes into scaffold of triphenylamine (TPA)-based ligands was developed to improve the visible-light absorption, enhance the oxidation potentials of ground states, and decrease the reduction potentials of excited states, providing a powerful tool for the continuous modulation of photoelectronic property of metal-organic framework (MOF)-based heterogeneous photocatalyst. And the ligand inserted with two thiophenes was found to possess well-balanced photoelectronic performance, endowing the corresponding MOF Zn–BCTA with good visible light-harvesting ability and moderate excited-state reduction potential with minimal over-potential for the photoineduced generation of sulfonyl radicals while avoiding the competitive over-reduction of sulfonyl moieties. The break of C3-symmetry of TPA-based ligand forged the distorted coordination geometry of Zn4O nodes of MOF to provide potential active sites to facilitate the fixation and activation of α,β‐unsaturated carbonyl substrates, and the two-fold interpenetrated frameworks further enhanced the spatial proximity between the encapsulated substrate and the photoredox-active centre. The synergy of well-tuned photoelectronic property of Zn–BCTA and spatial confinement effect within pores benefited the tandem sulfonylation-cyclisation of unsaturated alkenes in an efficient and diastereoselective mode for the construction of biointeresting sulphoyl isoquinolinediones/oxindoles.

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Publication details

The article was received on 14 Aug 2018, accepted on 11 Oct 2018 and first published on 12 Oct 2018


Article type: Paper
DOI: 10.1039/C8NJ04151B
Citation: New J. Chem., 2018, Accepted Manuscript
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    Thiophene insertion for continuously modulating photoelectronic property of triphenylamine-based metal-organic framework for photocatalytic sulfonylation-cyclisation of activated alkenes

    T. Zhang, Y. Shi, S. Zhang, C. Jia, C. He and C. Duan, New J. Chem., 2018, Accepted Manuscript , DOI: 10.1039/C8NJ04151B

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