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

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 (L2−L4) 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 (3−5) to 2D (6−9) 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 4−10 in the solid state have
been studied.

本研究致力于对基于嘧啶的硫醚配体几何形状及反离子的整体分子结构影响进行系统性的探究。通过合成含有N原子的大环二硫醚配体2,6-双(2-嘧啶硫基甲基)吡啶(L1)及其三种结构相关的同分异构体双(2-嘧啶硫基甲基)苯(L2−L4)，我们基于CuX(X = I, Br, Cl, SCN, 或 CN)的自组装以及四种结构相关的柔性二硫醚配体，成功合成了10种新的金属有机实体，包括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, 和 {[Cu6I5(L4)3](BF4)·H2O}n 10。这些化合物的合成与表征通过元素分析、红外光谱和X射线晶体学完成。单晶X射线分析显示，这10种Cu(I)配合物从0维(1和2)到1维(3−5)再到2维(6−9)直至3维(10)呈现出逐渐增加的维度，这表明配体几何形状在Cu(I)配合物的框架形成中扮演着至关重要的角色。同时，还研究了反离子及π-π弱相互作用对这些配位聚合物形成及维度的影响。此外，对固态下Cu(I)配位聚合物4−10的发光特性进行了研究。