Photooxidase Mimicking with Adaptive Coordination Molecular Capsules.

ABSTRACT

One important feature of enzyme catalysis is the induced-fit conformational change after binding substrates. Herein, we report a biomimetic water-soluble molecular capsule featuring adaptive structural change toward substrate binding, which offers an ideal platform for efficient photocatalysis. The molecular capsule was coordination-assembled from three anthracene-bridged bis-TPT [TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine] ligands and six (bpy)Pd(NO3)2 (bpy = 2,2'-bipyridine). Once substrates bind to its hydrophobic cavity, this capsule would undergo quantitative capsule-to-bowl transformation. Visible-light absorption brought about by both the anthracene units and the charge-transfer absorption on the late-formed quintuple π-π stacked host-guest complex efficiently facilitates aerobic photooxidation for the sulfide guests by visible-light irradiation under mild conditions. Desired turnover numbers and product selectivity (sulfoxide over sulfone) have been achieved by the transformable nature of the catalyst and the hydrophilicity of the sulfoxide product. Such a photocatalytic process enabled by an adaptive coordination capsule and substrates as the allosteric effector paves the way for constructing artificial systems to mimic enzyme catalysis.