Solvent-Dependent Supramolecular Host-Guest Assemblies of Platinum(II) Tweezers and a Guest System: From Discrete Molecules to High-Ordered Oligomers.

A series of platinum(II) calix[4]arene-based molecular tweezers was synthesized. The studies of the host-guest association with a charge-neutral cyclometalated platinum(II) complex showed a drastic color change and the turning on of near-infrared emission resulting from Pt⋅⋅⋅Pt and π-π interactions. Control of the host-guest assembly process by varying the solvent composition can lead to a change from discrete host and guest molecules to high-ordered host-guest oligomers with the formation of sheet-like nanostructures, demonstrating a rare example of three-state supramolecular host-guest system with high solubility in solvents of diverse polarity. The change in host-guest assembly behaviors could be probed by drastic color changes from yellow to orange to green. The present study provides insights into the systematic design of solvent-responsive molecular materials using molecular tweezers-directed host-guest assembly, with potential applications in colorimetric sensing of changes in the micro-environment.