Mixed-Valence CuI/CuIII Metal–Organic Frameworks with Non-innocent Ligand for Multielectron Transfer

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

doi:10.1002/anie.202312494

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

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

Nanomaterials Chemistry Group

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

Abstract

We report two novel three-dimensional copper-benzoquinoid metal–organic frameworks (MOFs), [Cu₄L₃]_n and [Cu₄L₃ ⋅ Cu(iq)₃]_n (LH₄=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.

Original language	English
Article number	e202312494
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	50
DOIs	https://doi.org/10.1002/anie.202312494
State	Published - Dec 11 2023

Funding

This work was supported by the Ministry of Science and Technology (MOST) of Taiwan under grants MOST 111-2113-M-006-007 (to T.-H. C.) and MOST 111-2221-E-006-011-MY3 (to W. K.). This work was also financially supported by the Hierarchical Green-Energy Materials (Hi-GEM) Research Center, from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) and MOST (MOST 110-2634-F-006-020) in Taiwan (to W. K.). This research was supported in part by High Education Sprout Project, MOE of the Headquarters of University Advancement at NCKU (to T.-H. C. and W. K.). The simulation work by A. I. and the work by I. P. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Separation Science program, and Materials Chemistry program under award no DE-SC00ERKCG21. This research used resources of the Computer and Data Environment for Science (CADES) at Oak Ridge National Laboratory, managed by UT-Battelle, LLC for the U.S. DOE under contract DE-AC05-00OR22725. The authors gratefully acknowledge the use of ESCA000200, EA000600, EM000800, and XRD003100 of MOST 108-2731-M-006-001 belonging to the Core Facility Center of NCKU. The authors are indebted to Dr. Ting-Shen Kuo (National Taiwan Normal University) for the collection and the refinement of crystallographic data. The authors would like to thank the Instrumentation Center at National Tsing Hua University for assistance with the EPR measurements. This manuscript has been authored in part by UT-Battelle, LLC, under contract DE-AC05-00OR22725 with the US DOE. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe-public-access-plan). This work was supported by the Ministry of Science and Technology (MOST) of Taiwan under grants MOST 111‐2113‐M‐006‐007 (to T.‐H. C.) and MOST 111‐2221‐E‐006‐011‐MY3 (to W. K.). This work was also financially supported by the Hierarchical Green‐Energy Materials (Hi‐GEM) Research Center, from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education (MOE) and MOST (MOST 110‐2634‐F‐006‐020) in Taiwan (to W. K.). This research was supported in part by High Education Sprout Project, MOE of the Headquarters of University Advancement at NCKU (to T.‐H. C. and W. K.). The simulation work by A. I. and the work by I. P. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Separation Science program, and Materials Chemistry program under award no DE‐SC00ERKCG21. This research used resources of the Computer and Data Environment for Science (CADES) at Oak Ridge National Laboratory, managed by UT‐Battelle, LLC for the U.S. DOE under contract DE‐AC05‐00OR22725. The authors gratefully acknowledge the use of ESCA000200, EA000600, EM000800, and XRD003100 of MOST 108‐2731‐M‐006‐001 belonging to the Core Facility Center of NCKU. The authors are indebted to Dr. Ting‐Shen Kuo (National Taiwan Normal University) for the collection and the refinement of crystallographic data. The authors would like to thank the Instrumentation Center at National Tsing Hua University for assistance with the EPR measurements. This manuscript has been authored in part by UT‐Battelle, LLC, under contract DE‐AC05‐00OR22725 with the US DOE. The US government retains and the publisher, by accepting the article for publication, acknowledges that the US government retains a nonexclusive, paid‐up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for US government purposes. DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe‐public‐access‐plan).

Funders	Funder number
DOE Public Access Plan
Data Environment for Science
LLC
Separation Science program	DE‐SC00ERKCG21
U.S. Department of Energy	108-2731-M-006-001, EM000800, DE‐AC05‐00OR22725, EA000600, XRD003100, ESCA000200
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Ministry of Education	MOST 110‐2634‐F‐006‐020
UT-Battelle
Ministry of Science and Technology, Taiwan	111‐2113‐M‐006‐007, 111‐2221‐E‐006‐011‐MY3
National Cheng Kung University Hospital
National Tsing Hua University
National Taiwan Normal University

Keywords

Cu(I)/Cu(III)
Metal–Organic Frameworks
Mixed-Valence
Non-innocent Ligand
Redox Chemistry

Access to Document

10.1002/anie.202312494

Cite this

Fu, S. Y., Chang, C. H., Ivanov, A. S., Popovs, I., Chen, J. L., Liao, Y. F., Liu, H. K., Chirra, S., Chiang, Y. W., Lee, J. C., Liu, W. L., Kaveevivitchai, W., & Chen, T. H. (2023). Mixed-Valence Cu^I/Cu^III Metal–Organic Frameworks with Non-innocent Ligand for Multielectron Transfer. Angewandte Chemie - International Edition, 62(50), Article e202312494. https://doi.org/10.1002/anie.202312494

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title = "Mixed-Valence CuI/CuIII Metal–Organic Frameworks with Non-innocent Ligand for Multielectron Transfer",

abstract = "We report two novel three-dimensional copper-benzoquinoid metal–organic frameworks (MOFs), [Cu4L3]n and [Cu4L3 ⋅ Cu(iq)3]n (LH4=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.",

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AU - Fu, Shang Yuan

AU - Chang, Cheng Han

AU - Ivanov, Alexander S.

AU - Popovs, Ilja

AU - Chen, Jeng Lung

AU - Liao, Yen Fa

AU - Liu, Hsin Kuan

AU - Chirra, Suman

AU - Chiang, Yun Wei

AU - Lee, Jui Chin

AU - Liu, Wei Ling

AU - Kaveevivitchai, Watchareeya

AU - Chen, Teng Hao

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N2 - We report two novel three-dimensional copper-benzoquinoid metal–organic frameworks (MOFs), [Cu4L3]n and [Cu4L3 ⋅ Cu(iq)3]n (LH4=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.

AB - We report two novel three-dimensional copper-benzoquinoid metal–organic frameworks (MOFs), [Cu4L3]n and [Cu4L3 ⋅ Cu(iq)3]n (LH4=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.

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