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- Title
Mixed‐Valence Cu<sup>I</sup>/Cu<sup>III</sup> Metal–Organic Frameworks with Non‐innocent Ligand for Multielectron Transfer.
- Authors
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
- 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.
- Subjects
METAL-organic frameworks; COPPER; VALENCE (Chemistry)
- Publication
Angewandte Chemie, 2023, Vol 135, Issue 50, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202312494