Supramolecular Assembly of Triangulo Pd(II) Diimine Complexes Containing Triply‐Bridging Sulfide Ligands

Abstract We report here a substituent effect of diimines on the solid‐state assembly of interesting triangulo Pd(II) complexes, [(Pd(d‐ t ‐bpy)) 3 (μJ 3 ‐S) 2 ][NO 3 ] 2 1 ·[NO 3 ] 2 and [(Pd(bpy)) 3 (μ 3 ‐S) 2 ][ClO 4 ] 2 2 ·[ClO 4 ] 2 (d‐ t ‐bpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine, bpy = 2,2′‐bipyridine). 2 ·[ClO 4 ] 2 shows the intermolecular π···π interactions leading to the formation of one‐dimensional frameworks, whereas 1 ·[NO 3 ] 2 only shows the discrete structure in the solid state, featuring an interesting herring‐bone arrangement. The variation in structural motifs from 1 ·[NO 3 ] 2 to 2 ·[ClO 4 ] 2 is expected to be dominated by the substituent's steric hindrance for the diimine ligand. Thus, the crystal‐engineering approach has proved successful in the solid‐state packing due to a substituent's modification of the diimine ligand.