Interfacial photocatalysis over hierarchical porous donor-π-acceptor tetrathienoanthracene-based conjugated microporous polymers for visible-light-driven aerobic organic oxidation.

Photocatalytic aerobic organic synthesis offers a sustainable, atom-economic pathway to produce high-value chemicals and reduces the high energy consumption of conventional thermal catalytic processes. Conventional inorganic semiconductor photocatalysts are restricted by narrow visible-light response, rapid charge carrier recombination, limited structural modulation and weak cycling durability. Herein, two donor-π-acceptor (D-π-A) functional hierarchical porous conjugated microporous polymers (CMPs), namely TTA-TPT-CMP and TTA-TPA-CMP, are rationally constructed via bottom-up Sonogashira-Hagihara cross-coupling.Tetrathienoanthracene (TTA), a robust electron-donor building block, is conjugated to two distinct acceptors via alkyne π-linkers, namely 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TPT) and tris(4-ethynylphenyl)amine (TPA). The constructed hierarchical porous architecture integrates intrinsic micropores and interparticle mesopores, endowing the CMP materials with abundant exposed active sites and unimpeded mass-transport channels for organic substrates and reactive oxygen species. Comprehensive characterizations confirm that TTA-TPT-CMP possesses widened visible-light harvesting capacity, accelerated charge separation and transfer, suppressed carrier recombination, and outstanding molecular oxygen activation ability to yield superoxide radicals (O2•-) and singlet oxygen (1O2). Operated at ambient temperature under 24 W 460 nm blue LED irradiation with atmospheric air as the sole oxidant, TTA-TPT-CMP serves as an efficient and durable metal-free photocatalyst. It achieves selective oxidation of thioethers and aerobic cyclization for benzothiazole synthesis with maximum product yields of 99%, together with broad substrate applicability and remarkable tolerance toward various functional groups. Additionally, the catalyst retains prominent catalytic performance over eight consecutive cycling tests. This work establishes a universal molecular modulation strategy for high-performance D-π-A conjugated microporous polymers and constructs a low-energy, recyclable heterogeneous photocatalytic platform for visible-light-driven aerobic synthesis, offering fundamental insights into interfacial charge and oxygen activation behavior of porous organic photocatalysts.