Acetic Acid Induced Self-Assembly of Supramolecular Compounds\n[Et<sub>4</sub>N]<sub>3</sub>[(WS<sub>4</sub>Cu<sub>2</sub>)<sub>2</sub>(μ-CN)<sub>3</sub>]·2MeCN and [PPh<sub>4</sub>][WS<sub>4</sub>Cu<sub>3</sub>(μ-CN)<sub>2</sub>]·MeCN from\nPreformed Clusters [A]<sub>2</sub>[WS<sub>4</sub>(CuCN)<sub>2</sub>] (A = Et<sub>4</sub>N, PPh<sub>4</sub>)
Jian-Ping Lang (1406386)Chang-Mei Jiao (2682964)Shan-Bao Qiao (2682967)Wen-Hua Zhang (1406392)Brendan F. Abrahams (1605808)
Abstract
Reactions of two preformed trinuclear W/Cu/S clusters, [A]<sub>2</sub>[WS<sub>4</sub>(CuCN)<sub>2</sub>] (<b>1</b>: A = Et<sub>4</sub>N; <b>2</b>: A = PPh<sub>4</sub>), with\ndifferent concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et<sub>4</sub>N]<sub>3</sub>[(WS<sub>4</sub>Cu<sub>2</sub>)<sub>2</sub>(μ-CN)<sub>3</sub>]·2MeCN (<b>3</b>), and [PPh<sub>4</sub>][WS<sub>4</sub>Cu<sub>3</sub>(μ-CN)<sub>2</sub>]·MeCN (<b>4</b>), respectively. Compound <b>4</b> can also be readily obtained\nin a high yield from the reaction of <b>2</b> with equimolar [Cu(MeCN)<sub>4</sub>]PF<sub>6</sub> in MeCN. These compounds have been\ncharacterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray\nanalysis reveals that compound <b>3</b> retains the WS<sub>4</sub>Cu<sub>2</sub> cluster core, which serves as a 3-connecting node to link\nequivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound <b>4</b> consists of a T-shaped\nWS<sub>4</sub>Cu<sub>3</sub> core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or\ndouble cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of <b>3</b>\nand <b>4</b> from the two cluster precursors <b>1</b> and <b>2</b> suggests that this simple synthetic strategy is likely to be applicable\nto many related systems.
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