Crystal structure, magnetic properties and molecular orbital calculations of a binuclear copper(II) complex bridged by an alkoxo-oxygen atom and an acetate ion
JOURNAL OF MOLECULAR STRUCTURE, cilt.693, sa.1-3, ss.225-234, 2004 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 693 Sayı: 1-3
- Basım Tarihi: 2004
- Doi Numarası: 10.1016/j.molstruc.2004.02.037
- Dergi Adı: JOURNAL OF MOLECULAR STRUCTURE
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
- Sayfa Sayıları: ss.225-234
- Anahtar Kelimeler: dinuclear copper(II) complex, magnetic properties, antiferromagnetic coupling, ab initio restricted Hartree-Fock molecular orbital calculation, TRANSITION-METAL DIMERS, ANTIFERROMAGNETIC INTERACTIONS, EXCHANGE INTERACTIONS, LIGANDS
- Ankara Üniversitesi Adresli: Hayır
Özet
[Cu-2(L)(O2CMe)].(C3H7NO) (L = 1,3-bis(2,hydroxy-3-meythoxybenzlidene)propan-2-ol) was synthesized and its crystal structure determined. (C21H22N2O7Cu2).(C3H7NO) monoclinic, space group P2(1)/c, a = 9.7670(10), b = 21.059(2), c = 12.5750(10) Angstrom, beta = 92.308(8)degrees, V = 2584.4(4) Angstrom(3), Z = 4. The Cu(II) ions are linked by the alkoxide oxygen of the Schiff base ligand on the oxygen atoms of the acetate ion. The (CuCu)-Cu-... distance and Cu-O-Cu angle are 3.154(2) Angstrom and 107.0(2)degrees, respectively. Temperature-dependent magnetic susceptibility measurements of the complex show an intramolecular antiferromagnetic coupling in the dimeric Cu(II) core. The super-exchange coupling constant (-2J) is 185.4 cm(-1). Ab initio restricted Hartree-Fock (RHF) and semi-empirical extended Huckel molecular orbital calculations were performed for the explanation of the significant differences in antiferromagnetic interactions between homologous mu-alkoxo and acetate bridged dicopper(II) complexes. Ab initio restricted RHF calculations have shown that the acetate bridge and alkoxide bridge contribute to the magnetic interaction countercomplementary to reduce antiferromagnetic interaction. (C) 2004 Elsevier B.V. All rights reserved.