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.