Multi-stimuli Control over Assembly and Guest Binding in Metallo-supramolecular Hosts Based on Dithienylethene Photoswitches.

It is difficult to assemble multi-component metallo-supramolecular architectures in a non-statistical fashion, which limits their development toward functional materials. Herein, we report a system of interconverting bowls and cages that are able to respond to various selective stimuli (light, ligands, anions), based on the self-assembly of a photochromic dithienylethene (DTE) ligand, La, with PdII cations. By combining the concept of "coordination sphere engineering", relying on bulky quinoline donors, with reversible photoswitching between the ligand's open (o-La) and closed (c-La) forms, a [Pd2(o-La)4] cage (o-C) and a [Pd2(c-La)3] bowl (c-B) were obtained, respectively. This structural rearrangement modulates the system's guest uptake capabilities. Among three bis-sulfonate guests (G1, G2, and G3), the cage can encapsulate only the smallest (G1), while the bowl binds all of them. Bowl c-B was further used to synthesize a series of heteroleptic cages, [Pd2LA3LB], representing a motif never reported before. Additional ligands (Lc-f), with short or long arms, tune the cavity size, thus enabling or preventing guest uptake. Addition of Br-/Ag+ makes it possible to change the overall charge, again triggering guest uptake and release, as well as fourth ligand de-/recomplexation. In combination, site-selective introduction of functionality and application of external stimuli lead to an intricate system of hosts with different guest preferences. A high degree of complexity is achieved through cooperativity between only a few components.