Ligand‐field effect to harness the magnetic anisotropy in a series of mixed valence Co (III)–Co (II) dinuclear complexes

Three mixed valence dinuclear Co (III)–Co (II)‐based complexes having general formulae of [CoIICoIII (HL2)2(L1)] [L1H = 2‐hydroxy‐1‐naphthaldehyde (1), o‐vanillin (2), and salicylaldehyde (3)] have been synthesized successfully using Schiff base (LH4) ligand. The complexes were characterized by sing...

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Veröffentlicht in:Applied organometallic chemistry 2024-05, Vol.38 (5), p.n/a
Hauptverfasser: Manohar, Ezhava Manu, Guizouarn, Thierry, Ahmed, Naushad, Herchel, Radovan, Pointillart, Fabrice, Das, Sourav, Dey, Atanu
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Sprache:eng
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Zusammenfassung:Three mixed valence dinuclear Co (III)–Co (II)‐based complexes having general formulae of [CoIICoIII (HL2)2(L1)] [L1H = 2‐hydroxy‐1‐naphthaldehyde (1), o‐vanillin (2), and salicylaldehyde (3)] have been synthesized successfully using Schiff base (LH4) ligand. The complexes were characterized by single‐crystal XRD, powder XRD, IR, and UV–Vis analyses. The CoII ion with elongated octahedral geometry conferred significant magnetic anisotropy with D values being 64.0(8), 71.1(7), and 52.1(3) cm−1 for 1, 2, and 3, respectively. These complexes exhibited single‐molecule magnet behavior with magnetic relaxation occurring mainly through Raman for 1 and 3 whereas direct and Raman for complex 2. The analysis of the static and dynamic magnetic properties was further supported by theoretical calculations using CASSCF/DLPNO‐NEVPT2. Three Co (III)–Co (II) mixed valence dinuclear complexes were synthesized and characterized using various techniques. These complexes exhibited elongated octahedral geometry around Co (II) ion, significant magnetic anisotropy, and field‐induced single‐molecule magnet behavior with magnetization relaxation through Raman, Orbach, and direct processes. The analysis of magnetic properties was complemented by theoretical calculations.
ISSN:0268-2605
1099-0739
DOI:10.1002/aoc.7441