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](2)MS2O2 (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(mu-bpY)(2)center dot Sol](n) (M = Mo, Sol = 1.3DMF center dot 5.5H(2)O 1; M = W, Sol = 1.5DMF center dot 8.2H(2)O 2), [MoOS3Cu3(NCS)(bPY)(mu-bpy)(2)center dot DMF](n) (3), and [WOS3Cu3(NCS) (mu-bpy)(2.5) center dot 3DMP](n) (4). Polymer 1 or 2 crystallizes in the Fddd space group with a 2-fold interpenetrating (10,3)-6 net, which presents a 3-connected 3D heterothiometallic polymer assembled with bidentate organic bridging ligands. Polymer 3 crystallizes in the space group PI with a 2D noninterpenetrating network with (6,3) topology in which [MoOS3Cu3(bpy)] units are interconnected via three single or double Cu-mu-bpy-Cu bridges. Polymer 4 crystallizes in the space group C2/c with a (6(4) 8(2)) 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.