Understanding the Structural Modulations in Twisted Donor–Acceptor–Donor (D-A-D) Systems for Boosting Type I Photosensitizing Photocatalytic Activity

Supramolecular assemblies based on the twisted donor–acceptor–donor (D-A-D) building block Qx-Ind have been developed, which interestingly, due to the balanced angle of twist (38.28°), high intermolecular charge transfer, and crystallization induced emission (CIE) characteristics, exhibit high molar absorptivity and a long-lived “lighted” excited state at the supramolecular level. The validity of the design concept was examined by preparing CIE active D-A-D system Qx-Indaz (weak donor, low angle of twist: 35.45°), in which, due to the insertion of an additional binding site for noncovalent interactions, a drastic change in the photophysical behavior is observed. The combined spectroscopic studies of all the compounds unveil the strong impact of modulation of the angle of twist and intermolecular charge transfer upon photophysical behavior in the aggregated state. Due to the favorable photophysical behavior, the supramolecular assemblies of Qx-Ind exhibit high type I photosensitizing activity in comparison to Qx-Indaz. The superior type I photosensitizing activity of Qx-Ind assemblies is manifested in their ability to efficiently catalyze the aerobic oxidative synthesis of quinazolin-4(3H)-ones (via type I ROS) from 2-aminobenzamide and aromatic aldehydes in the absence of additional additives (base/oxidant). Unlike photocatalytic nanoassemblies reported in the literature, due to the CIE characteristics, Qx-Ind does not require preliminary preparation and could be directly introduced in the solid state to reaction media. Thus, the present work demonstrates a simple strategy of upgrading type I photosensitizing activity by improving the ground/excited state behavior of a twisted D-A-D system through modulation of the angle of twist and charge transfer characteristics.