Tunable Isometric Donor–Acceptor Wurster‐Type Covalent Organic Framework Photocathodes

Abstract 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 −2 at 0.2 V RHE ) 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.