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• W2942983355 endingPage "7053" @default.
• W2942983355 startingPage "7044" @default.
• W2942983355 abstract "Semiquinoid radical bridging ligands are capable of mediating exceptionally strong magnetic coupling between spin centers, a requirement for the design of high-temperature magnetic materials. We demonstrate the ability of sulfur donors to provide much stronger coupling relative to their oxygen congeners in a series of dinuclear complexes. Employing a series of chalcogen donor-based bis(bidentate) benzoquinoid bridging ligands, the series of complexes [(TPyA)2Cr2(RL4–)]2+ (OLH4 = 1,2,4,5-tetrahydroxybenzene, OSLH4 = 1,2-dithio-4,5-dihydroxybenzene, SLH4 = 1,2,4,5-tetrathiobenzene, TPyA = tris(2-pyridylmethyl)amine) was synthesized. Variable-temperature dc magnetic susceptibility data reveal the presence of weak antiferromagnetic superexchange coupling between CrIII centers in these complexes, with exchange constants of J = −2.83(3) (OL4–), –2.28(5) (OSL4–), and −1.80(2) (SL4–) cm–1. Guided by cyclic voltammetry and spectroelectrochemical measurements, chemical one-electron oxidation of these complexes gives the radical-bridged species [(TPyA)2Cr2(RL3–•)]3+. Variable-temperature dc susceptibility measurements in these complexes reveal the presence of strong antiferromagnetic metal–semiquinoid radical coupling, with exchange constants of J = −352(10) (OL3–•), – 401(8) (OSL3–•), and −487(8) (SL3–•) cm–1. These results provide the first measurement of magnetic coupling between metal ions and a thiosemiquinoid radical, and they demonstrate the value of moving from O to S donors in radical-bridged metal ions in the design of magnetic molecules and materials." @default.
• W2942983355 created "2019-05-09" @default.
• W2942983355 creator A5015741289 @default.
• W2942983355 creator A5050917541 @default.
• W2942983355 creator A5086170310 @default.
• W2942983355 date "2019-04-29" @default.
• W2942983355 modified "2023-10-17" @default.
• W2942983355 title "Thiosemiquinoid Radical-Bridged Cr^III₂ Complexes with Strong Magnetic Exchange Coupling" @default.
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• W2942983355 doi "https://doi.org/10.1021/acs.inorgchem.9b00674" @default.
• W2942983355 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/31034214" @default.
• W2942983355 hasPublicationYear "2019" @default.
• W2942983355 type Work @default.

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