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Issue 22, 2017
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Magneto-structural correlations in a family of di-alkoxo bridged chromium dimers

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Abstract

A series of di-alkoxo bridged Cr(III) dimers have been synthesised using pyridine alcohol ligands. The structures fall into four general categories and are of formula: [Cr2(OMe)2(pic)4]·½MeOH·½Et2O (1), [Cr2(hmp)2(pic)2X2] (where X = Cl (2), Br (3)), [Cr2(L)2Cl4(A)2]·2S (where L = hmp, A = H2O and S = Et2O (4); L = hmp, A = pyridine and S = pyridine (5); L = hmp, A = 4-picoline and no S (6); L = hep, A = H2O and S = MeCN (7)), and [Cr(hmp)(hmpH)Cl2]·MeCN (8). Direct current (DC) magnetic susceptibility measurements show relatively weak antiferromagnetic exchange interactions between the Cr(III) centres with J values <|15| cm−1 in all of the complexes measured. DFT calculations performed on complexes 1–8 reproduce both the sign and strength of the exchange interactions found experimentally, and confirm that the magnitude and sign of the J value is strongly dependent upon the orientation of the dihedral angle formed between the bridging Cr2O2 plane and the O–R vector of the bridging group (θ), and the Cr–O–Cr–O dihedral angle (ψ).

Graphical abstract: Magneto-structural correlations in a family of di-alkoxo bridged chromium dimers

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Publication details

The article was received on 03 Apr 2017, accepted on 08 May 2017 and first published on 08 May 2017


Article type: Paper
DOI: 10.1039/C7DT01197K
Citation: Dalton Trans., 2017,46, 7159-7168
  • Open access: Creative Commons BY license
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    Magneto-structural correlations in a family of di-alkoxo bridged chromium dimers

    H. W. L. Fraser, G. S. Nichol, G. Velmurugan, G. Rajaraman and E. K. Brechin, Dalton Trans., 2017, 46, 7159
    DOI: 10.1039/C7DT01197K

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