External Template-Assisted Self-Assembly:Design and Synthesis of 4,4′-bipy-Based Mo(W)/Cu/S Heterothiometallic Polymeric Clusters Directed by 1,1′-Bis(pyridinium)methylene Cation

Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = Cl, NCS) in the present of 1,1-bis(pyridinium)methylene [bpm = 1,1′-bis(pyridinium)methylene] resulted in four novel neutral heterothiometallic cluster polymers based on tetranuclear [Mo/WOS3Cu3] unit: [MOS3Cu3Cl(μ-bpy)2·Sol]n (M = Mo, Sol = 1.3DMF·5.5H2O 1; M = W, Sol = 1.5DMF·8.2H2O 2), [MoOS3Cu3(NCS)(bpy)(μ-bpy)2·DMF]n (3), and [WOS3Cu3(NCS)(μ-bpy)2.5·3DMF]n (4). Polymer 1 or 2 crystallizes in the Fddd space group with a 2-fold interpenetrating (10,3)-b net, which presents a 3-connected 3D heterothiometallic polymer assembled with bidentate organic bridging ligands. Polymer 3 crystallizes in the space group P1 with a 2D noninterpenetrating network with (6,3) topology in which [MoOS3Cu3(bpy)] units are interconnected via three single or double Cu-μ-bpy-Cu bridges. Polymer 4 crystallizes in the space group C2/c with a (64 82) net, which displays the first self-interpenetrating network in heterothiometallic chemistry. All of these results confirm the ideal template effect and correct choice of bpm.