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Different crystal structures and luminescent properties of zinc and cadmium coordination polymers constructed from two flexible thioether ligands with different alkyl chains
Authors:Hua-Ze Dong  Jian Zhao  Shao-Hua Gou  Hai-Bin Zhu
Affiliation:1. School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China;2. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, China
Abstract:Treatments of nitrogen-containing heterocyclic dithioether ligands, 1,2-bis(4-(pyridin-3-yl) pyrimidin-2-ylthio) ethane (L1) and 1,3-bis (4-(pyridin-3-yl) pyrimidin-2-ylthio) propane (L2), with zinc or cadmium salts have resulted in the interesting frameworks with structural motifs from a mononuclear macrocycle or a dinuclear macrocycle to an one-dimensional structure. A small difference of the alkyl length between L1 and L2 led to conspicuous changes of the fluorescent properties of both ligands and their complexes. Mainly due to the size of metal atoms, structures of [ZnL2I2] (1) and [CdL2I2] (2) are varied from a mononuclear macrocycle to a 1D framework, while {[ZnL2(H2O)4](ClO4)2}2 (3) and {[CdL2(H2O)4](ClO4)2}2 (4) are dinuclear macrocycles in which perchlorate anions may play an important template role. As for complexes 58 ([ZnL1I2]n (5), [CdL1I2]n (6), {{[ZnL12(H2O)4](ClO4)2}0.5 · L10.5 · CH3OH} (7), {{[Cd0.5L1(H2O)2](ClO4)}2 · CH3OH · L1} (8)), the self-assemble processes were mainly directed by the organic ligand in the reactions of L1 with metal salts. Complexes 14 exhibit blue fluorescence emissions, among which 1 and 2 may be suitable as candidates for blue fluorescent materials.
Keywords:Flexible thioether ligands   Luminescence properties   Structure elucidation   Thermogravimetric analysis
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