Precise Modulation of Molecular Building Blocks from Tweezers to Rectangles for Recognition and Stimuli-Responsive Processes.

Alkynylplatinum(II) terpyridine complexes have been increasingly explored since the previous decades, mainly arising from their intriguing photophysical properties and aggregation affinities associated with their extensive Pt(II)···Pt(II) and π-π stacking interactions. Through molecular engineering, one can modulate their fundamental properties and assembly behavior by introduction of various functional groups and structural features. They can therefore serve as ideal candidates to construct metal complex-based molecular architectures to provide an alternative to organic compounds. The metal-based framework can be simultaneously built from predetermined building blocks, giving rise to their well-defined, unique, and discrete natures for molecular recognition. The individual constituents can contribute to molecular architectures with their integrated properties, allowing the manipulation of the various noncovalent intermolecular forces and interactions for selective guest capture. In this Account, our recent progress in the development of these metallomolecular frameworks based on the alkynylplatinum(II) terpyridine system and their recognition properties toward different guest molecules will be presented. Phosphorescent molecular tweezers have been constructed from the alkynylplatinum(II) terpyridine moiety to demonstrate host-guest interactions with cationic, charge-neutral and anionic platinum(II), palladium(II), gold(I), and gold(III) complexes and their binding affinities were found to be perturbed by different metal···metal, π-π and electrostatic interactions. The host-guest assembly process has also resulted in dramatic color changes, together with the turning on of near-IR (NIR) emissions as a result of extensive Pt(II)···Pt(II) interactions. Further work has also been performed to demonstrate that the tweezers can selectively recognize π-surfaces of different planar π-conjugated organic guests. The framework of molecular tweezers has been extended to a double-decker tweezers structure, or a triple-decker structure, which can bind two equivalents of square-planar platinum(II) guests cooperatively to induce a significant color change in solution, representing rare examples of discrete Magnus' green-like salts. By the approaches of structural modifications, we have further modulated the host architecture from molecular tweezers to molecular rectangles. The rectangles have been found to show selective encapsulation of different transition metal complex guests based on the size and steric environment of the host cavity. The molecular rectangles also exhibit reversible host-guest association, in which guest capture and ejection processes can be manipulated by the pH environment, illustrating a potential approach for precise and smart delivery of therapeutic reagents to the slightly more acidic cancer cells.