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Increasing Structure Dimensionality of Copper(I) Complexes by Varying the Flexible Thioether Ligand Geometry and Counteranions

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posted on 15.05.2006, 00:00 by Rong Peng, Dan Li, Tao Wu, Xiao-Ping Zhou, Seik Weng Ng
This work focuses on the systematic investigation of the influences of pyrimidine-based thioether ligand geometries and counteranions on the overall molecular architectures. A N-containing heterocyclic dithioether ligand 2,6-bis(2-pyrimidinesulfanylmethyl)pyridine (L1) and three structurally related isomeric bis(2-pyrimidinesulfanylmethyl)benzene (L2L4) ligands have been prepared. On the basis of the self-assembly of CuX (X = I, Br, Cl, SCN, or CN) and the four structurally related flexible dithioether ligands, we have synthesized and characterized 10 new metal−organic entities, Cu4(L1)2I4 1, Cu4(L1)2Br4 2, [Cu2(L2)2I2·CH3CN]n 3, [Cu(L3)I]n 4, [Cu(L3)Br]n 5, [Cu(L3)CN]n 6, [Cu(L4)CN]n 7, [Cu2(L4)I2]n 8, [Cu2(L4)(SCN)2]n 9, and {[Cu6I5(L4)3](BF4)·H2O}n 10, by elemental analyses, IR spectroscopy, and X-ray crystallography. Single-crystal X-ray analyses show that the 10 Cu(I) complexes possess an increasing dimensionality from 0D (1 and 2) to 1D (35) to 2D (69) to 3D (10), which indicates that the ligand geometry takes an essential role in the framework formation of the Cu(I) complexes. The influence of counteranions and π−π weak interactions on the formation and dimensionality of these coordination polymers has also been explored. In addition, the photoluminescence properties of Cu(I) coordination polymers 410 in the solid state have been studied.