Mixed‐Valence Cu I /Cu III Metal–Organic Frameworks with Non‐innocent Ligand for Multielectron Transfer

Fu, Shang‐Yuan; Chang, Cheng‐Han; Ivanov, Alexander S.; Popovs, Ilja; Chen, Jeng‐Lung; Liao, Yen‐Fa; Liu, Hsin‐Kuan; Chirra, Suman; Chiang, Yun‐Wei; Lee, Jui‐Chin; Liu, Wei‐Ling; Kaveevivitchai, Watchareeya; Chen, Teng‐Hao

doi:10.1002/anie.202312494

Mixed‐Valence Cu ^I /Cu ^III Metal–Organic Frameworks with Non‐innocent Ligand for Multielectron Transfer

Journal Article · Mon Sep 25 00:00:00 EDT 2023 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202312494· OSTI ID:2005002

Fu, Shang‐Yuan ^[1]; Chang, Cheng‐Han ^[2]; Ivanov, Alexander S. ^[3]; Popovs, Ilja ^[3]; Chen, Jeng‐Lung ^[4]; Liao, Yen‐Fa ^[4]; Liu, Hsin‐Kuan ^[5]; Chirra, Suman ^[1]; Chiang, Yun‐Wei ^[6]; Lee, Jui‐Chin ^[5]; Liu, Wei‐Ling ^[2]; ^[1]; ^[7]

Department of Chemical Engineering Hierarchical Green-Energy Materials (Hi-GEM) Research Center National Cheng Kung University Tainan City 70101 Taiwan
Department of Chemistry Tamkang University New Taipei City 25137 Taiwan
Chemical Sciences Division Oak Ridge National Laboratory P.O. Box 2008 Oak Ridge TN 37831 USA
National Synchrotron Radiation Research Center Hsinchu 30076 Taiwan
Core Facility Center National Cheng Kung University Tainan City 70101 Taiwan
Department of Chemistry National Tsing Hua University Hsinchu 300-044 Taiwan
School of Pharmacy, College of Medicine National Cheng Kung University Tainan City 70101 Taiwan

Abstract

We report two novel three‐dimensional copper‐benzoquinoid metal–organic frameworks (MOFs), [Cu ₄ L ₃ ] _n and [Cu ₄ L ₃ ⋅ Cu(iq) ₃ ] _n (LH ₄ =1,4‐dicyano‐2,3,5,6‐tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal–organic extended solids. The coordination between the mixed‐valence metal and redox‐non‐innocent ligand L, which promotes through‐bond charge transfer between Cu metal sites, allows better metal‐ligand orbital overlap of the d‐π conjugation, leading to strong long‐range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly‐covalent Cu(III), non‐innocent ligand, and pore environments of these bench stable Cu(III)‐containing frameworks on multielectron transfer and electrochemical properties.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2005002

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 50 Vol. 62; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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