title: Sodium-centered dodecanuclear Co(II) and Ni(II) complexes with 2-(phosphonomethylamino)succinic acid: studies of spectroscopic, structural, and magnetic properties.
abstract: Two new isostructural cobalt(II) and nickel(II) polynuclear complexes with 2-(phosphonomethyl)aminosuccinic acid, H4PMAS, namely, Na[Co12(PMAS)6(H2O)17(OH)]·x2H2O, 1·x2H2O, and Na[Ni12(PMAS)6(H2O)17(OH)]·xH2O, 2·xH2O, have been synthesized for the first time from aqueous solutions and studied by single crystal X-ray diffraction, infrared, and UV-visible diffuse reflectance spectroscopy; TG/DTA analysis; and magnetochemistry. Both 1 and 2 crystallize in the rhombohedral crystal system with the R3[overline] space group with 1/6 of the Co12(PMAS)6 or Ni12(PMAS)6 moieties in the asymmetric unit. The X-ray refinements reveal the presence of 18 water sites, but unit cell charge balance requires that one water molecule must be an OH(-) anion, an anion which is disordered over the 18 sites. The PMAS(4-) ligand forms two five-membered and one six-membered chelation ring. Both 1 and 2 contain 24-membered metallacycles as a result of the bridging nature of the PMAS(4-) ligands. The resulting three-dimensional structures have one-dimensional channels with a sodium cation at the center of symmetry. The temperature dependence of the magnetic susceptibility reveals the presence of weak antiferromagnetic exchange coupling interactions in both 1 and 2. Two exchange coupling constants, J1 = -15.3(7) cm(-1) and J2 = -1.06(2) cm(-1) with S1 = S2 = 3/2 for the Co(1)···Co(1) and Co(1)···Co(2) exchange pathways, respectively, are required for 1, and J1 = -1.17(6) cm(-1) and J2 = -4.00(8) cm(-1) with S1 = S2 = 1 for the Ni(1)···Ni(1) and Ni(1)···Ni(2) exchange pathways, respectively, are required for 2, in order to fit the temperature dependence of the observed magnetic susceptibilities.
authors.affiliation: V. I. Vernadsky Institute of General and Inorganic Chemistry, Ukrainian National Academy of Sciences, 03680, Kyiv 142, Akademika Palladina Ave. 32/34, Ukraine. andriy.gudima@yahoo.com
authors.forename: Andriy O
authors.initials: AO
authors.lastname: Gudima
authors.forename: Ganna V
authors.initials: GV
authors.lastname: Shovkova
authors.forename: Olena K
authors.initials: OK
authors.lastname: Trunova
authors.forename: Fernande
authors.initials: F
authors.lastname: Grandjean
authors.forename: Gary J
authors.initials: GJ
authors.lastname: Long
authors.forename: Nikolay
authors.initials: N
authors.lastname: Gerasimchuk
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D059346:Magnets / Q000737:chemistry; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D063065:Organophosphonates / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D019802:Succinic Acid / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D063065:Organophosphonates; D003035:Cobalt; D009532:Nickel; D019802:Succinic Acid