Charge Separation in Metal-Organic Framework Enables Heterogeneous Thiol Catalysis

Shengxian Cheng; Jing Ouyang; Muqing Li; Yingxue Diao; Jiachen Yao; Fengxing Li; Yat-For Lee; Herman Ho-Yung SUNG; Ian Williams; Zhengtao Xu; Yangjian Quan

doi:10.1002/anie.202300993

Charge Separation in Metal-Organic Framework Enables Heterogeneous Thiol Catalysis

Shengxian Cheng, Jing Ouyang, Muqing Li, Yingxue Diao, Jiachen Yao, Fengxing Li, Yat-For Lee, Herman Ho-Yung SUNG, Ian Williams, Zhengtao Xu^*, Yangjian Quan^*

^*Corresponding author for this work

Department of Chemistry

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

32 Citations (Scopus)

Abstract

Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr-TPDCS-1, consisting of Zr₆-clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′-tetramercapto[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr₆-cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram-scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl-radical catalysis. © 2023 Wiley-VCH GmbH.

Original language	English
Article number	e202300993
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	25
Online published	19 Apr 2023
DOIs	https://doi.org/10.1002/anie.202300993
Publication status	Published - 19 Jun 2023

Funding

Y.Q. acknowledges the start-up fund from HKUST (Project No. R9804). Z.X. acknowledges a GRF grant from the Research Grants Council of HKSAR (CityU 11307120).

Research Keywords

HAT
Heterogeneous Catalysis
Hybrid Materials
MOF
Thiyl Radical

RGC Funding Information

RGC-funded

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10.1002/anie.202300993

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title = "Charge Separation in Metal-Organic Framework Enables Heterogeneous Thiol Catalysis",

abstract = "Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr-TPDCS-1, consisting of Zr6-clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′-tetramercapto[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6-cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram-scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl-radical catalysis. {\textcopyright} 2023 Wiley-VCH GmbH.",

keywords = "HAT, Heterogeneous Catalysis, Hybrid Materials, MOF, Thiyl Radical",

author = "Shengxian Cheng and Jing Ouyang and Muqing Li and Yingxue Diao and Jiachen Yao and Fengxing Li and Yat-For Lee and SUNG, {Herman Ho-Yung} and Ian Williams and Zhengtao Xu and Yangjian Quan",

year = "2023",

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doi = "10.1002/anie.202300993",

language = "English",

volume = "62",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons",

number = "25",

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TY - JOUR

T1 - Charge Separation in Metal-Organic Framework Enables Heterogeneous Thiol Catalysis

AU - Cheng, Shengxian

AU - Ouyang, Jing

AU - Li, Muqing

AU - Diao, Yingxue

AU - Yao, Jiachen

AU - Li, Fengxing

AU - Lee, Yat-For

AU - SUNG, Herman Ho-Yung

AU - Williams, Ian

AU - Xu, Zhengtao

AU - Quan, Yangjian

PY - 2023/6/19

Y1 - 2023/6/19

N2 - Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr-TPDCS-1, consisting of Zr6-clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′-tetramercapto[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6-cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram-scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl-radical catalysis. © 2023 Wiley-VCH GmbH.

AB - Photoinduced metal–organic framework (MOF) enabled heterogeneous thiol catalysis has been achieved for the first time. MOF Zr-TPDCS-1, consisting of Zr6-clusters and TPDCS linkers (TPDCS=3,3′′,5,5′′-tetramercapto[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylate), effectively catalyzed the borylation, silylation, phosphorylation, and thiolation of organic molecules. Upon irradiation, the fast electron transfer from TPDCS to Zr6-cluster is believed to facilitate the formation of the thiyl radical, a hydrogen atom transfer catalyst, which competently abstracts the hydrogen from borane, silane, phosphine, or thiol for generating the corresponding element radical to engender the chemical transformations. The elaborate control experiments evidenced the generation of thiyl radicals in MOF and illustrated a radical reaction pathway. The gram-scale reaction worked well, and the product was conveniently separated via centrifugation and vacuum with a turnover number (TON) of ≈3880, highlighting the practical application potential of heterogeneous thiyl-radical catalysis. © 2023 Wiley-VCH GmbH.

KW - HAT

KW - Heterogeneous Catalysis

KW - Hybrid Materials

KW - MOF

KW - Thiyl Radical

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U2 - 10.1002/anie.202300993

DO - 10.1002/anie.202300993

M3 - RGC 21 - Publication in refereed journal

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 25

M1 - e202300993

ER -

Charge Separation in Metal-Organic Framework Enables Heterogeneous Thiol Catalysis

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GRF: Pre-Concentrating and Detecting Natural-Water Heavy Metals by Sulfur-Equipped Porous Crystals

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Charge Separation in Metal-Organic Framework Enables Heterogeneous Thiol Catalysis

Abstract

Funding

Research Keywords

RGC Funding Information

Access Output

Other Access Options

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Other Files and Links

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GRF: Pre-Concentrating and Detecting Natural-Water Heavy Metals by Sulfur-Equipped Porous Crystals

Cite this