Abstract
<h2>Summary</h2> As an analog of graphene, carbon nitrides have drawn increasing attention, ranging from artificial photosynthesis to synthetic organic chemistry. Notably, the most studied polymeric, C<sub>3</sub>N<sub>4</sub>, and other stoichiometric ones, such as C<sub>3</sub>N<sub>5</sub>, C<sub>4</sub>N<sub>3</sub>, and C<sub>3</sub>N, are commonly employed repetitive units of six-membered rings. Building blocks of five-membered rings (FMRs) are also fascinating and prevalent from a fundamental point of view, but FMR-based carbon nitrides are scarcely reported. Here, we propose a stable FMR-based C<sub>3</sub>N<sub>2</sub> and the kinetic-oriented synthesis method via a pre-stabilization strategy using abundant-available zeolitic imidazolate framework as a precursor. The FMR topological structure and the associated dangling bonds were disclosed in C<sub>3</sub>N<sub>2</sub>, leading to an interesting p-π conjugation and splitting molecular orbitals, which remarkably narrowed the optical bandgap unusually down to 0.81 eV. The as-obtained C<sub>3</sub>N<sub>2</sub> was further successfully applied to real-time, dynamic, and quantitative photoelectrochemical biosensing for practical non-transparent biosamples under near-infrared light irradiation.
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