Coordination-driven self-assembly of 2D-metallamacrocycles using a shape-selective PtII2-organometallic 90° acceptor: design, synthesis and sensing study

Abstract

Synthesis of a series of two-dimensional metallamacrocycles via coordination-driven self-assembly of a shape-selective Pt^II₂-molecular building unit incorporating carbazole-ethynyl functionality is described. An equimolar (1 : 1) combination of a Pt^II₂-organometallic 90° acceptor, 1, with rigid linear ditopic donors (L_a and L_b) afforded [4 + 4] self-assembled octanuclear molecular squares, 2 and 3, in quantitative yields, respectively [L_a = 4,4′-bipyridine; L_b = trans-1,2-bis(4-pyridyl)ethylene]. Conversely, a similar treatment of 1 with an amide-based unsymmetrical flexible ditopic donor, L_c, resulted in the formation of a [2 + 2] self-sorted molecular rhomboid (4a) as a single product [L_c = N-(4-pyridyl)isonicotinamide]. Despite the possibility of several linkage isomeric macrocycles (rhomboid, triangle and square) due to the different connectivity of L_c, the formation of a single and symmetrical molecular rhomboid (4a) as the only product is an interesting observation. All the self-assembled macrocycles (2, 3 and 4a) were fully characterized by multinuclear NMR (¹H and ³¹P) and ESI-MS analysis. Further structural insights about the size and shape of the macrocycles were obtained through energy minimization using density functional theory (DFT) calculations. Decoration of the starting carbazole building unit with Pt-ethynyl functionality enriches the assemblies to be more π-electron rich and luminescent in nature. Macrocycles 2 and 3 could sense the presence of electron deficient nitroaromatics in solution by quenching of the initial intensity upon gradual addition of picric acid (PA). They exhibited the largest quenching response with high selectivity for nitroaromatics compared to several other electron deficient aromatics tested.