Issue 46, 2023

Experimental and computational study of the exchange interaction between the V(iii) centers in the vanadium-cyclal dimer

Abstract

[V2(HCyclal)2] is prepared by controlled oxidation of vanadium nanoparticles at 50 °C in toluene. The V(0) nanoparticles are synthesized in THF by reduction of VCl3 with lithium naphthalenide. They exhibit very small particle sizes of 1.2 ± 0.2 nm and a high reactivity (e.g. with air or water). By reaction of V(0) nanoparticles with the azacrown ether H4Cyclal, [V2(HCyclal)2] is obtained with deep green crystals and high yield. The title compound exhibits a V(III) dimer (V⋯V: 304.1(1) pm) with two deprotonated [HCyclal]3− ligands as anions. V(0) nanoparticles as well as the sole coordination of V(III) by a crown ether as the ligand and nitrogen as sole coordinating atom are shown for the first time. Magnetic measurements and computational results point to antiferromagnetic coupling within the V(III) couple, establishing an antiferromagnetic spin S = 1 dimer with the magnetic susceptibility determined by the thermal population of the total spin ranging from ST = 0 to ST = 2.

Graphical abstract: Experimental and computational study of the exchange interaction between the V(iii) centers in the vanadium-cyclal dimer

Supplementary files

Article information

Article type
Paper
Submitted
03 Oct 2023
Accepted
01 Nov 2023
First published
03 Nov 2023
This article is Open Access
Creative Commons BY license

Dalton Trans., 2023,52, 17389-17397

Experimental and computational study of the exchange interaction between the V(III) centers in the vanadium-cyclal dimer

A. Reiß, M. K. Reimann, C. Jin, M. Wachter-Lehn, R. K. Kremer, R. Pöttgen, K. Fink, W. Klopper and C. Feldmann, Dalton Trans., 2023, 52, 17389 DOI: 10.1039/D3DT03243D

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