Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive Metal–Organic Frameworks
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jacs.9b04822.pdf
Description
Accepted version
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1.04 MB
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Adobe PDF
Checksum (MD5)
1ff77e2530f1c378da205b8333c5eca6
Author(s)
Yang, Luming
He, Xin
Dinca, Mircea
Date Issued
June 2019
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Yang, Luming et al. "Triphenylene-Bridged Trinuclear Complexes of Cu: Models for Spin Interactions in Two-Dimensional Electrically Conductive Metal–Organic Frameworks." Journal of the American Chemical Society 141, 26 (June 2019): 10475–10480 © 2019 American Chemical Society
Version
Author's final manuscript
Abstract
Reaction of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) and 2,3,6,7,10,11-hexaaminotriphenylene (HATP) with [Cu(Me3tacn)]2+ (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) produces trigonal tricopper complexes [(Me3tacnCu)3(HOTP)]3+ (1) and [(Me3tacnCu)3(HITP)]4+ (2) (HOTP, HITP = hexaoxy- and hexaiminotriphenylene, respectively). These trinuclear complexes are molecular models for spin exchange interactions in the two-dimensional conductive metal-organic frameworks (MOFs) copper hexaoxytriphenylene (Cu3HOTP2) and copper hexaiminotriphenylene (Cu3HITP2). Whereas complex 1 is isolated with HOTP3- bearing the same oxidation state as found in the oxy-bridged MOF, the triply oxidized HITP3- found in Cu3HITP2 is unstable with respect to disproportionation in the molecular model. Indeed, magnetic measurements reveal ligand-centered radical character for 1 and a closed-shell structure for 2, in agreement with the redox state of the ligands. All neighboring spins are antiferromagnetically coupled in 1 and 2. These results help probe metal-ligand-metal interactions in conductive MOFs and provide potential inspiration for the synthesis of other two-dimensional materials with delocalized electrons.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/jacs.9b04822
