Multi‐Component Coordination‐Driven Self‐Assembly: Construction of Alkyl‐Based Structures and Molecular Modelling

The design of supramolecular coordination complexes (SCCs) is typically predicated on the use of rigid molecular building blocks through which the structural outcome is determined based on the number and orientation of labile coordination sites on metal acceptors, and the angularity of the ligand donors that are to bridge these nodes. Three‐component systems extend the complexity of self‐assembly by utilizing two different Lewis base donors in concert with a metal that favors a heteroligated coordination environment. The thermodynamic preference for heteroligation provides a new design principle to the formation of SCCs, wherein multicomponent architectures need not employ only rigid donors. Herein, we exploit the self‐selection processes of bis(phosphine) Pt II metal centers which favor mixed Pt(pyridyl)(carboxylate) coordination spheres over their homoligated counterparts, specifically using alkyl‐based dicarboxylate ligands instead of traditionally rigid phenyl, alkenyl, or ethynyl variants. Using this mode of assembly, flexible‐based 2D and 3D SCCs containing long alkyl chains were synthesized and characterized. Density functional theory (DFT) and natural population analysis (NPA) calculations were performed on model systems to probe the thermodynamic preference for heteroligated coordination spheres in the experimental systems.