| 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(μJ3‐S)2]NO3]2 1 ·NO3]2 and (Pd(bpy))3(μ3‐S)2]ClO4]2 2 ·ClO4]2 (d‐t‐bpy = 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine, bpy = 2,2′‐bipyridine). 2 ·ClO4]2 shows the intermolecular π···π interactions leading to the formation of one‐dimensional frameworks, whereas 1 ·NO3]2 only shows the discrete structure in the solid state, featuring an interesting herring‐bone arrangement. The variation in structural motifs from 1 ·NO3]2 to 2 ·ClO4]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. |
