Synthesis, characterization and magnetic properties of a dinuclear oxidovanadium(IV) complex: Magneto-structural DFT studies on the effects of out-of-plane -OCH₃ angle

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• 作者：Nader Noshiranzadeh^a ; Marzieh Emami^a ; Rahman Bikas^a ; ^{bikas_r@yahoo.com} ; Joaquin Sanchiz^b ; ^{jasnchiz@ull.es} ; Marta Otręba^c ; Pavlo Aleshkevych^d ; Tadeusz Lis^c
• 关键词：Dinuclear oxidovanadium(IV) ; Magnetic studies ; X-ray structure ; DFT calculation ; Magneto-structural studies
• 刊名：Polyhedron
• 出版年：2017
• 出版时间：28 January 2017
• 年：2017
• 卷：122
• 期：Complete
• 页码：194-202
• 全文大小：1919 K
• 卷排序：122

文摘

A new dinuclear oxidovanadium(IV) complex with a symmetric heptadentate N4O3-donor ligand, [V2(O)2L(μ-OCH3)] CH3OH (1), was synthesized and characterized by elemental analysis, spectroscopic methods (FT-IR, UV–Vis and EPR) and single crystal X-ray analysis, where H3L is the Schiff base ligand obtained by the condensation of triethylenetetramine and 5-bromosalicylaldehyde. Single crystal X-ray analysis indicated that the vanadium(IV) ions have distorted octahedral geometry and are connected together by phenoxy and methoxy bridging groups. The EPR and magnetic susceptibility measurements show weak V⋯V antiferromagnetic interactions. The analysis of the magnetic susceptibility data with the Bleaney–Bowers equation gave a value for the magnetic coupling constant of J = −1.60 cm−1 (H = −JS1S2). A Broken-Symmetry DFT study also agreed with an intramolecular character of the magnetic coupling giving a comparable value for J and showed an important dependence of the magnetic interaction with the out-of-plane shift of the methyl group of the methoxy bridging group.