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Di- and Tri-nuclear V$^{III}$ and Cr$^{III}$ Complexes of Dipyridyltriazoles: Ligand Rearrangements, Mixed Valency and Ferromagnetic Coupling

Rinck, J.; Kitchen, J. A.; Carter, A. B.; Lan, Y.; Anson, C. E.; Fink, K.; Brooker, S.; Powell, A. K.

Abstract:
The first dinuclear and trinuclear chromium(III) and dinuclear vanadium(III) complexes of N$^{4}$-R-substituted-3,5-di(2-pyridyl)-1,2,4-triazole (Rdpt) ligands have been prepared by solvothermal complexations under inert atmospheres, and characterized. The reactions of Cr$^{III}$ and V$^{III}$ with adpt (R = amino) resulted in deamination of the ligand and yielded the dinuclear doubly-triazolate bridged complexes [V$_{2}^{III}$(dpt$^{-}$)$_{2}$Cl$_{4}$] (1) and [Cr$_{2}^{III}$(dpt$^{-}$)$_{2}$Cl$_{4}$] (2). In the case of the Cr$^{III}$ complex 2 this bridging results in a rare example of ferromagnetic coupling for a dinuclear Cr$^{III}$ compound. DFT studies confirm that in 2 the ferromagnetic coupling pathways dominate over the antiferromagnetic pathways, whereas in 1 the reverse occurs, consistent with the observed overall antiferromagnetic coupling in that case. It was also found that the use of different additives in the reaction allows the nuclearity of the Cr$^{III}$ product to be manipulated, giving either the dinuclear system, or the first example of a trinuclear circular helicate for a Rdpt complex, [Cr$_{3}^{III}$(dpt)$_{3}$Cl$_{6}$]·1¾MeCN·¼DCM (3). ... mehr

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Verlagsausgabe §
DOI: 10.5445/IR/1000122968
Veröffentlicht am 08.09.2020
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 09.07.2020
Sprache Englisch
Identifikator ISSN: 2296-2646
KITopen-ID: 1000122968
HGF-Programm 43.21.04 (POF III, LK 01) Molecular Engineering
Erschienen in Frontiers in Chemistry
Verlag Frontiers Media
Band 8
Seiten Art.Nr. 540
Nachgewiesen in Dimensions
Web of Science
Scopus
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