Energy‐level Rule Guided Construction of Low‐Coordinated LnOFs for Redox‐Gated and Programmable Low‐Bias Electrochemiluminescence

Abstract Electrochemiluminescence (ECL) platforms are often constrained by aggregation‐caused quenching (ACQ), inefficient charge transfer, and instability under high driving potentials, thereby limiting their sensitivity and reproducibility. Herein, an energy‐level rule‐guided strategy is reported to construct a distinctive lanthanide‐organic framework (LnOF), [Tb 2 ( µ 2 ‐OH) 2 (TBAPy)], through the controlled self‐assembly of Tb 3+ and 4,4′,4″,4‴‐(pyrene‐1,3,6,8‐tetrayl)tetrabenzoic acid (H 4 TBAPy). This LnOF features the rod‐shaped [Tb( µ 2 ‐OH) 2 (‐CO 2 ) 2 ] chains, a large π ‐stacking distance (6.685 Å) between pyrene rings, and a 3D sea topology, effectively suppressing ACQ and antenna‐type energy transfer from the TBAPy triplet state to Tb 3+ , thereby preserving pyrene‐based fluorescence while inhibiting the luminescence of Tb 3+ . Importantly, the low‐coordinated [TbO 6 ] octahedron exposes multiple open metal sites to coordinate with coreactant S 2 O 8 2− and facilitate its decomposition to SO 4 •− radicals during electrochemical reactions. This process markedly reduces interfacial resistance and enables robust low‐bias ECL amplification. Furthermore, a MnO 2 interfacial gate enables ratiometric ECL OFF/ON switching upon glutathione reduction, delivering internally referenced signal outputs with an ultralow limit of detection of 6.8 × 10 −4 n m across a wide range (0.01–500 n m ). This kind of functional material design establishes a generalizable blueprint for LnOF‐based ECL systems, advancing programmable and low‐bias luminescent sensing with exceptional sensitivity and stability.