Anion recognition of chloride and bromide by a rigid dicobalt(II) cryptate |
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Authors: | Chen Jia-Mei Zhuang Xiao-Mei Yang Li-Zi Jiang Long Feng Xiao-Long Lu Tong-Bu |
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Institution: | 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. |
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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. |
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