Syntheses, crystal structures and electron paramagnetic resonance studies of CoII- and MnII-coordination polymers with the twisted ligand di(4-pyridyl)disulfide in double bridge fashion
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Add time:07/18/2019 Source:sciencedirect.com
Four coordination polymers, {[Co2(4-DPSS)4(DMF)4](ClO4)4}n (1), {[Mn2(4-DPSS)4(DMF)4](ClO4)4}n (2), {[Co(4-DPSS)2(H2O)(NO3)]NO3·3H2O}n (3) and [Co(4-DPSS)2(NCS)2]n (4) have been synthesized to study the reactivity of cobalt(II) and manganese(II) salts (perchlorate, thiocyanate and nitrate) with the flexible ligand di(4-pyridyl)disulfide (4-DPSS). These compounds have repeated rhomboidal structures in which the di(4-pyridyl)disulfide ligands coordinate the metal centers in a double bridged fashion. Each double chain and the metallocycle cavities are chiral and contain either the M- or the P-enantiomeric forms of 4-DPSS and are independent on recrystallization solvents or the metallic precursors. The crystal packing of these coordination polymers reveals that, in all cases, weak interactions such as classical and non-classical hydrogen bonds, as well as S⋯S interactions, connect the polymeric chains to increase the dimensionality of the network. Low temperature electron paramagnetic resonance (EPR) measurements on powdered samples show that the transition-metal ions, Co (II) and Mn (II) ions, are in the high spin states S = 3/2 and 5/2, respectively, and adopt octahedral geometry in case of compounds 1, 2 and 3, and rhombic environment in case of 4.
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