Mo(W)/Cu/S Cluster-Based Supramolecular Arrays Assembled from Preformed Clusters [Et<sub>4</sub>N]<sub>4</sub>[WS<sub>4</sub>Cu<sub>4</sub>I<sub>6</sub>] and [(<i>n</i>-Bu)<sub>4</sub>N]<sub>2</sub>[MoOS<sub>3</sub>Cu<sub>3</sub>X<sub>3</sub>] (X = I, SCN) with Flexible Ditopic Ligands
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In our working toward the rational design and synthesis of cluster-based suppramolecular architectures, a set of new [WS4Cu4]- or [MoOS3Cu3]-based supramolecular assemblies have been prepared from reactions of preformed cluster compounds [Et4N]4[WS4Cu4I6] (1) and [(n-Bu)4N]2[MoOS3Cu3X3] (2, X = I; 3, X = SCN) with flexible ditopic ligands such as dipyridylsulfide (dps), dipyridyl disulfide (dpds), and their combinations with dicyanamide (dca) anion and 4,4‘-bipy. The cluster precursor 1 reacted with dps or dpds and sodium dicyanamide (dca) in MeCN to produce [WS4Cu4I2(dps)3]·2MeCN (4·2MeCN) and [WS4Cu4(dca)2(dpds)2]·Et2O·2MeCN (5·Et2O·2MeCN), respectively. On the other hand, treatment of 2 with dpds in DMF/MeCN afforded [MoOS3Cu3I(dpds)2]·0.5DMF·2(MeCN)0.5 (6·0.5DMF·2(MeCN)0.5) while reaction of 3 with sodium dicyanamide (dca) and 4,4‘-bipy in DMF/MeCN gave rise to [MoOS3Cu3(dca)(4,4‘-bipy)1.5]·DMF·MeCN (7·DMF·MeCN). Compounds 4·2MeCN, 5·Et2O·2MeCN, 6·0.5DMF·2(MeCN)0.5, and 7·DMF·MeCN have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray crystallography. Compound 4 contains a 2D layer array made of the saddle-shaped [WS4Cu4] cores interlinked by three pairs of Cu−dps−Cu bridges. Compound 5 has another 2D layer structure in which the [WS4Cu4] cores are held together by four pairs of Cu−dca−Cu and Cu−dpds−Cu bridges. Compound 6 displays a 1D spiral chain structure built of the nido-like [MoOS3Cu3] cores via two pairs of Cu−dpds−Cu bridges. Compound 7 consists of a 2D staircase network in which each [MoOS3Cu3(4,4‘-bipy)]2 dimeric unit interconnects with four other equivalent units by a pair of 4,4‘-bipy ligands and two pairs of dca anions. The [WS4Cu4] core in 4 or 5 and the [MoS3Cu3] core in 7 show a planar 4-connecting node and a seesaw-shaped 4-connecting node, respectively, which are unprecedented in cluster-based supramolecular compounds. The successful assembly of 4−7 from the three cluster precursors 1−3 through flexible ditopic ligands provides new routes to the rational design and construction of complicated cluster-based supramolecular arrays.
