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Magneto-structural correlations in a family of di-alkoxo bridged chromium dimers.

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·½Et2 O (1), [Cr2 (hmp)2 (pic)2 X2 ] (where X = Cl (2), Br (3)), [Cr2 (L)2 Cl4 (A)2 ]·2S (where L = hmp, A = H2 O and S = Et2 O (4); L = hmp, A = pyridine and S = pyridine (5); L = hmp, A = 4-picoline and no S (6); L = hep, A = H2 O 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 Cr2 O2 plane and the O-R vector of the bridging group (θ), and the Cr-O-Cr-O dihedral angle (ψ).

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