The photocyclization of alkynylanilines catalyzed by an aggregated PtII-based octahedral cage has been shown to mimic bio-enzyme catalysis by aggregated biological macromolecules. The aggregated supramolecular species exhibits a higher photocatalytic efficiency than dispersed metal-organic cages without aggregation.
Enzymes facilitate chemical conversions through the collective activity of aggregated components, but the marriage of aggregation-induced emission (AIE) with molecular containers to emulate enzymatic conversion remains challenging. Herein, we report a new approach to construct a PtII-based octahedral cage with AIE characteristics for the photocyclization of alkynylaniline by restricting the rotation of the pendant phenyl rings peripheral to the PtII corner. With the presence of water, the C−H⋅⋅⋅π interactions involving the triphenylphosphine fragments resulted in aggregation of the molecular cages into spherical particles and significantly enhanced the PtII-based luminescence. The kinetically inert Pt-NP chelator, with highly differentiated redox potentials in the ground and excited states, and the efficient coordination activation of the platinum corner facilitated excellent catalysis of the photocyclization of alkynylaniline. The enzymatic kinetics and the advantages of binding and activating substrates in an aqueous medium provide a new avenue to develop mimics for efficient photosynthesis.
Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Zhong Wei, Xu Jing, Yang Yang, Jiayou Yuan, Mingxu Liu, Cheng He, Chunying Duan