title: Anion recognition of chloride and bromide by a rigid dicobalt(II) cryptate.
abstract: The crystal structures of [Co 2L(Cl)](ClO 4) 3 ( 1), [Co 2L(Br)](ClO 4) 3 ( 2), [Co 2L(OH)(OH 2)]I 3 ( 3), and [Co 2L (1)(Cl)](ClO 4) 3 ( 4), the density functional theory calculations, as well as the binding constants of [Co 2L] (4+) toward Cl (-) and Br (-) and of [Co 2L (1)] (4+) toward Cl (-), are reported in this paper (L = N[(CH 2) 2NHCH 2(C 6H 4- p)CH 2NH(CH 2) 2] 3N, L (1) = N[(CH 2) 2NHCH 2(C 6H 4- m)CH 2NH(CH 2) 2] 3N). The rigid dicobalt(II) cryptate [Co 2L] (4+) shows the recognition of Cl (-) and Br (-) but not of F (-) and I (-), because of the size matching to its rigid cavity. We also found that the relative rigid tripodal skeleton of L than that of L (1) results in the higher affinity of [Co 2L] (4+) toward Cl (-). Magnetic susceptibility measurements of 1 and 2 indicate that the two Co(II) atoms in the cryptates are antiferromagnetically coupled through the Cl (-)/Br (-) bridge, with g = 2.19, J = -13.7 cm (-1) for 1, and g = 2.22, J = -17.1 cm (-1) for 2.
authors.affiliation: MOE Laboratory of Bioinorganic and Synthetic Chemistry, State Key Laboratory of Optoelectronic Materials and Technologies, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou, China.
authors.forename: Jia-Mei
authors.initials: JM
authors.lastname: Chen
authors.forename: Xiao-Mei
authors.initials: XM
authors.lastname: Zhuang
authors.forename: Li-Zi
authors.initials: LZ
authors.lastname: Yang
authors.forename: Long
authors.initials: L
authors.lastname: Jiang
authors.forename: Xiao-Long
authors.initials: XL
authors.lastname: Feng
authors.forename: Tong-Bu
authors.initials: TB
authors.lastname: Lu
mesh_terms: D000838:Anions / Q000737:chemistry; D001965:Bromides / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D043844:Crown Ethers / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D013816:Thermodynamics
chemical_list: D000838:Anions; D001965:Bromides; D002712:Chlorides; D043844:Crown Ethers; D003035:Cobalt