Construction of Thiadiazole-Bridged sp²-Carbon-Conjugated Covalent Organic Frameworks with Diminished Excitation Binding Energy Toward Superior Photocatalysis

Sp(2)-carbon-conjugated covalent organic frameworks (sp(2)c-COFs) have emerged as promising platforms for phototo-chemical energy conversion due to their tailorable optoelectronic properties, in-plane pi-conjugations, and robust structures. However, the development of sp(2)c-COFs in photocatalysis is still highly hindered by their limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp(2)c-COF (sp(2)c-COF-ST) synthesized by thiadiazole-mediated aldol-type polycondensation. The resultant sp(2)c-COF-ST demonstrates high chemical stability under strong acids and bases (12 M HCl or 12 M NaOH). The electro-deficient thiadiazole together with fully conjugated and planar skeleton endows sp(2)c-COF-ST with superior photoelectrochemical performance and charge-carrier separation and migration ability. As a result, when employed as a photocathode, sp(2)c-COF-ST exhibits a significant photocurrent up to similar to 14.5 mu A cm(-2) at 0.3 V vs reversible hydrogen electrode (RHE) under visible-light irradiation (>420 nm), which is much higher than those analogous COFs with partial imine linkages (mix-COF-SNT similar to 9.5 mu A cm(-2)) and full imine linkages (imi-COF-SNNT similar to 4.9 mu A cm(-2)), emphasizing the importance of the structure-property relationships. Further temperature-dependent photoluminescence spectra and density functional theory calculations demonstrate that the sp(2)c-COF-ST has smaller exciton binding energy as well as effective mass in comparison to mix-COF-SNT and imi-COF-SNNT, which suggests that the sp(2)c-conjugated skeleton enhances the exciton dissociation and carrier migration under light irradiation. This work highlights the design and preparation of thiadiazole-bridged sp(2)c-COFs with promising photocatalytic performance.