Coordination Polymers with π-Stacked Metalloparacyclophane Motifs: F-Shaped Mixed-Coordination Dinuclear Connectors

摘要

The design and construction of coordination polymers (CPs) composed of metal-ion connectors and linear organic -conjugated linkers are of great interest, owing to their use as functional materials.[1] One way in which their potential may be expanded is to prepare CPs having new structural motifs. With this idea in mind, face-to-face -stacked assemblies, such as paracyclophanes, are appealing building blocks for CPs, owing to their unique electronic properties arising from -orbital overlap.[2] Since the structural motifs of CPs are controlled by the number and orientation of the connector binding sites, the construction of the desired paracyclophane based CP frameworks requires the discovery of connectors with specific coordination characteristics. Herein, we describe a dinuclear connector having an unprecedented F shape, which arises from the close association of isovalent metal atoms with different coordination numbers and geometries. The propagation of the coordination geometry imposed by the mixed-coordination connector by using -conjugated linkers gives CP frameworks with -stacked metalloparacyclophanes as structural motifs. Furthermore, we show that these complex CP architectures can be obtained directly from their molecular components in a one-pot multicomponent approach, and we propose a mechanism for their construction.