A rare variety of self-assembledmolecular triangle [Pd₃(bpy)₃(imidazolate)₃](NO₃)₃, 1 is prepared by the combination of Pd(bpy)(NO3)2 with imidazole, at 1:1 ratio, in acetonitrile-water. Deprotonation of imidazole happened during the course of the complexation reaction where upon the metallomacrocycle is formed. The bowl-shaped trinuclear architecture of 1 is crafted with three peripheral bpy units capable of 𝜋 - 𝜋 stacking interactions. While the solution state structure of 1 can be best described as a trinuclear complex, in the solidstate well-fashioned intermolecular $\pi - \pi$ and CH-𝜋 interactions are observed. Thus, in the solid-state further self-assembly of already self-assembled molecular triangle is witnessed. The triangular panels are arranged in a linear manner utilizing intermolecular 𝜋 - 𝜋 interactions where upon two out of three bpy units of each molecule participated in the chain formation.

Self-assembled molecular triangles [Pd₃(phen)₃(imidazolate)₃](NO₃)₃, 1a and [Pd₃(phen)₃ (imidazolate)₃](PF₆)₃, 1b are prepared by the combination of imidazole with Pd(phen)(NO₃)₂ and Pd(phen) (PF₆)₂, respectively. Imidazole was deprotonated during the complexation reactions and the imidazolate so formed acted as a bis-monodentate bridging ligand to form the bowl-shaped trinuclear architectures of 1a/b. Relative orientation of the imidazolate moieties can be best described as syn,anti,anti as observed in the crystal structure of 1b. However, in solution state, slow conformational changes are assumed on the basis of ¹HNMR spectral data. The molecular triangles are crafted with three peripheral phen units capable of 𝜋−𝜋 stacking interactions. Well-fashioned intermolecular 𝜋−𝜋 interactions are observed in the solid-state, wherein further self-assembly of already self-assembled triangle is observed.