Tunable Isometric Donor-Acceptor Wurster-Type Covalent Organic Framework Photocathodes.

Covalent organic frameworks (COFs) offer remarkable versatility, combining ordered structures, high porosity, and tailorable functionalities in nanoscale reaction spaces. Herein, we report the synthesis of a series of isostructural, photoactive Wurster-type COFs achieved by manipulating the chemical and electronic nature of the Wurster aromatic amine building blocks. A series of donor-acceptor-donor (D-A-D) Wurster building block molecules was synthesized by incorporating heteroaromatic acceptors with varying strengths between triphenylamine donor groups. These tailored building blocks were integrated into a 2D COF scaffold, resulting in highly crystalline structures and similar morphologies across all COFs. Remarkably, this structural uniformity was also achieved in the synthesis of homogeneous and oriented thin films. Steady-state photoluminescence revealed a tunable red-shift in film emission exceeding 100 nm, demonstrating effective manipulation of their optical properties. Furthermore, photoelectrochemical (PEC) water splitting studies exhibited a doubled current density (8.1 μA cm at 0.2 V) for the COF with the strongest acceptor unit. These findings highlight the potential of Wurster D-A-D COFs in photoelectrochemical water splitting devices and pave the way for further exploration of chemical functionality-reactivity-property relationships in this promising class of photoactive materials.