title: Enhanced ferromagnetic interaction in metallacyclic complexes incorporating m-phenylenediamidato bridges.
abstract: The double stranded Cu(II)2-metallacyclic complex of formula [Cu2(mbpb)2].2H2O (1) and the triple stranded Ni(II)2-metallacyclic complexes of formula [Ni2(Hmbpb)3]PF6.21H2O (2), [Co(H2O)6][Ni2(mbpb)3)]THF.10H2O (3) and {Ag2(H2O)[Ni2(mbpb)3]}.11H2O (4) (where H2mbpb is the bisbidentate dinucleating bridging ligand 1,3-bis(pyridine-2-carboxamide) benzene) have been synthesised and characterised by single-crystal X-ray diffraction. Within the dinuclear molecules, metal ions are bridged by either fully or semideprotonated bisbidentate ligands, which are coordinated through the pyridine and amidato nitrogen donor atoms. In complex 4 the triple stranded dinuclear Ni2 units are connected to the Ag+ cations through O-amidato bridges and Ag-pi(benzene) interactions to afford a 1D bimetallic chain. Cu2 (1) and Ni2 (2-4) complexes exhibit ferromagnetic coupling between the metal ions through the bridging ligand with J(Cu-Cu) = 21.1 cm(-1) and J(Ni-Ni) in the range of 2.9-3.6 cm(-1), respectively. Amongst copper(II) dinuclear complexes bearing m-phenylenediamidato bridges, complex 1 exhibits the stronger ferromagnetic exchange coupling reported so far. DFT calculations firstly confirm that the spin polarisation mechanism is responsible for the ferromagnetic coupling, and secondly allows us to predict stronger ferromagnetic couplings in Cu(II)(2) complexes with larger tetrahedral distortions of the CuN4 coordination environment.
authors.affiliation: Departamento de Química Inorgánica, Universidad de Granada, 18071, Granada, Spain.
authors.forename: María A
authors.initials: MA
authors.lastname: Palacios
authors.forename: Antonio
authors.initials: A
authors.lastname: Rodríguez-Diéguez
authors.forename: Angelo
authors.initials: A
authors.lastname: Sironi
authors.forename: Juan Manuel
authors.initials: JM
authors.lastname: Herrera
authors.forename: Antonio J
authors.initials: AJ
authors.lastname: Mota
authors.forename: Joan
authors.initials: J
authors.lastname: Cano
authors.forename: Enrique
authors.initials: E
authors.lastname: Colacio
mesh_terms: D001555:Benzene Derivatives; D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008280:Magnetics; D008956:Models, Chemical; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines
chemical_list: C545910:(1,3-bis(pyridine-2-carboxamide) benzene); D001555:Benzene Derivatives; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D003300:Copper; D009532:Nickel