Organoplatinum(II)-Based Self-Complementary Molecular Tweezers with Guest-Induced Fluorochromic Behaviors

Cyclometalated organoplatinum(II) complexes have aroused tremendous interests due to their square-planar geometry and intriguing photophysics. To access multiplatinum systems with more than three cyclometalated organoplatinum(II) units, the traditional covalent synthetic approach suffers from tedious multistep reactions with low overall yield. In comparison, supramolecular assembly can be regarded as an effective strategy toward multiplatinum(II) architectures. Despite the progresses achieved, it is still challenging to fabricate well-ordered supramolecular assemblies with precise numbers of organoplatinum(II) units. Herein, self-complementary dimerized molecular tweezers with four cyclometalated platinum(II) units have been successfully constructed by taking advantage of dual roles of the incorporated 2,2':6',2''-terpyridine unit (serving as the rigid spacer and encapsulated guest). Furthermore, addition of electron-rich carbazoles leads to conversion of the self-complementary structure to molecular tweezer/guest complexes. Such a structural transformation gives rise to the concomitant luminescent color change. The unique guest-induced fluorochromic phenomena, which are seldom reported in the previous host-guest systems, would be promising as tunable luminescent and ratiometric sensing materials.