Construction of [(η⁵-C₅Me₅)WS₃Cu₃]-Based Supramolecular Compounds from Preformed Incomplete Cubane-Like Clusters [PPh₄][(η⁵-C₅Me₅)WS₃(CuX)₃] (X = CN, Br)

Approaches to the assembly of (η5-C5Me5)WS3Cu3-based supramolecular compounds from two preformed incomplete cubane-like clusters [PPh4][(η5-C5Me5)WS3(CuX)3] (X = CN, 1a; X = Br, 1b) have been investigated. Treatment of 1a with LiBr/1,4-pyrazine (1,4-pyz), pyridine (py), LiCl/py, or 4,4‘-bipyridine (4,4‘-bipy) and treatment of 1b with 4,4‘-bipy gave rise to a new set of W/Cu/S cluster-based compounds, [Li{((η5-C5Me5)WS3Cu3(μ3-Br))2(μ-CN)3}·C6H6]∞ (2), [(η5-C5Me5)WS3Cu3(μ-CN)2(py)]∞ (3), {[PPh4][(η5-C5Me5)WS3Cu3(μ3-Cl)(μ-CN)(CN)]·py}∞ (4), [PPh4]2[(η5-C5Me5)WS3Cu3(CN)2]2(μ-CN)2·(4,4‘-bipy) (5), and {[(η5-C5Me5)WS3Cu3Br(μ-Br)(4,4‘-bipy)]·Et2O}∞ (6). The structures of 2−6 have been characterized by elemental analysis, IR spectra, and single-crystal X-ray crystallography. Compound 2 displays a 1D ladder-shaped chain structure built of squarelike {[(η5-C5Me5)WS3Cu3(μ3-Br)(μ-CN)]4}(μ-CN)22- anions via two pairs of Cu−μ-CN−Cu bridges. Compound 3 consists of a single 3D diamondlike network in which each (η5-C5Me5)WS3Cu3 unit, serving as a tetrahedral node, interconnects with four other nearby units through Cu−μ-CN−Cu bridges. Compound 4 contains a 1D zigzag chain array made of cubane-like [(η5-C5Me5)WS3Cu3(μ3-Cl)(μ-CN)(CN)]- anions linked by a couple of Cu−μ-CN−Cu bridges. Compound 5 contains a dimeric structure in which the two incomplete cubane-like [(η5-C5Me5)WS3(CuCN)2(μ-CN)]- anions are strongly held together via a pair of Cu−μ-CN−Cu bridges. Compound 6 contains a 2D brick-wall layer structure in which dimers of [(η5-C5Me5)WS3Cu3Br(4,4‘-bipy)]2 are interconnected via four Cu−μ-Br−Cu bridges. The successful construction of (η5-C5Me5)WS3Cu3-based supramolecular compounds 2−6 from the geometry-fixed clusters 1a and 1b may expand the scope of the rational design and construction of cluster-based supramolecular assemblies.