External template-assisted self-assembly: design and synthesis of the [MoOS3Cu3]+ based supramolecular polymeric clusters

Abstract

Four novel heterothiometallic cluster polymers based on a [MoOS3Cu3] unit have been synthesized by the solution self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MoS2O2 and CuX (X = I, Br, or SCN) in the presence of different organic cation-templates [DMI]·I, [C6(Mim)2]·Br2, [C3(Mim)2]·Br2, and [BBP]·Br2: Compounds {[MoOS3Cu3I(μ-bpy)2.5]·2.5DMF}∞ (1), {[MoOS3Cu3I(μ-bpy)2.5] ·DMF}∞ (2), and {[MoOS3Cu3Br(μ-bpy)2.5]·2.5DMF}∞ (3) are isomorphous neutral 3D 4-fold interpenetrating architectures with a (6, 4) node, while polymer [MoOS3Cu3(NCS)(μ-bpy)2.5]∞ (4) is a 3D architecture with a (64 82) net displaying self-interpenetrating features. All of them have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and UV-vis. The results may provide fascinating insights into the template effect on the construction of the cluster-based coordination polymers.