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Cyanide‐Bridged [Co II 2 M II ] and [Co II 2 M II 2 ] Complexes Based on the [Co II (triphos)(CN) 2 ] Building Block: Syntheses, Structures, Magnetic Properties, and Density Functional Theoretical Studies
Author(s) -
Karadas Ferdi,
Shatruk Michael,
Perez Lisa M.,
Dunbar Kim R.
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201000128
Subject(s) - triphos , chemistry , cyanide , crystallography , cationic polymerization , metal , antiferromagnetism , ferromagnetism , inorganic chemistry , physics , organic chemistry , quantum mechanics , condensed matter physics
Two families of cationic cyanide‐bridged complexes, namely, {[Co(triphos)(CN) 2 ] 2 [M(MeOH) 4 ]}(ClO 4 ) 2 ([Co 2 M] M=Mn, Fe, Co, and Ni; triphos=1,1,1‐tris((diphenylphosphino)methyl)ethane) and {[Co(triphos)(CN) 2 ] 2 [M(MeOH) 4 ] 2 }(ClO 4 ) 4 ([Co 2 M 2 ] M=Mn and Ni) have been prepared from reactions of [Co II (triphos)(CN) 2 ] and M(ClO 4 ) 2 ⋅ 6H 2 O (M=Mn, Fe, Co, Ni) in methanol. The trinuclear complexes [Co 2 Mn], [Co 2 Fe], and [Co 2 Co], as well as both new tetranuclear complexes [Co 2 Mn 2 ] and [Co 2 Ni 2 ], exhibit antiferromagnetic coupling between metal centers. In contrast, the [Co 2 Ni] is characterized by ferromagnetic interactions between the Co II and Ni II centers. The magnetic behavior for these complexes was investigated by DFT calculations and was found to derive from overlap patterns of the different magnetic orbitals as influenced by the angles of the cyanide bridges.