Synthesis and density functional calculations of the new molecule-based magnet precursor [Fe(H2opba-i)(dmso)2]Cl

Journal of the Brazilian Chemical Society

Gilmar P. Souza²  Cibele Konzen¹  José D. Ardisson¹  Heitor A. De Abreu²  Hélio A. Duarte²  Antônio F. C. Alcântara²  Wallace C. Nunes¹  Waldemar A. A. Macedo¹  Marcelo Knobel¹  Humberto O. Stumpf² 

[1] ,Universidade Federal de Minas Gerais Instituto de Ciências Exatas Departamento de QuímicaBelo Horizonte MG ,Brazil

关键词: molecule-based magnet;    oxamate;    iron(III);    PBE/DZVP theoretical calculations;    cis/trans isomerism;   

DOI  :  10.1590/S0103-50532006000800008

来源: SciELO

【 摘 要 】

A new precursor of molecule-based magnetic systems, [Fe(H2opba-i)(dmso)2]Cl (1), with opba = ortho-phenylenebis(oxamato) in an iminoalcohol tautomeric form, was obtained as a product from the reaction between H4opba and FeCl3. Data from elemental analysis, IR and Mössbauer spectroscopies and magnetic measurements indicate that this precursor is composed of a mixture of trans (83%) and cis (17%) isomers. The chiMT value at 298K (2.1 emu K mol-1) corresponds to FeIII with spin state (S) between 3/2 and 5/2. Theoretical calculations (PBE/DZVP2) of trans- and cis-[Fe(H2opba-i)(dmso)2 ]+ show that both isomers have spin S = 1/2 in the ground state and S = 3/2 for the trans and S = 5/2 for the cis in the first excited state. The combination of these results leads to chiMT values of 0.375 and 2.3 emu K mol-1, at low and high temperature respectively, which are in accordance with the experimental data for 1.

【 授权许可】

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