CO(2)-enhanced TADF of an ultra-stable Cu(i) cluster via guest-host π-π interaction

通过客体-主体π-π相互作用增强CO(2)对超稳定Cu(I)簇的热激活延迟荧光(TADF)的影响

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Abstract

Efficient and reversible luminescence detection for CO(2) without solvent assistance is of great significance but remains challenging to achieve, due to the lack of efficient interaction between CO(2) molecules and the host emitting center. Benefiting from the abundant host-guest interactions, metal clusters provide a platform for detecting small molecules. However, the insufficient chemical stability of most metal clusters limits their practical applications. Here, we report a hydrophobic Cu(i) cluster (denoted as CuIDPO) with one-dimensional channels. Notably, it displays exceptional chemical stability in both acidic and alkaline aqueous solutions (pH = 1-14). More importantly, CuIDPO shows remarkable CO(2)-induced luminescence enhancement (up to 385% under 1 bar CO(2)), which can be applied to analyze CO(2) content (LOD = 7.7 mbar). Crystallographic analysis and theoretical calculations suggest the mechanism of CO(2)-locking rotation of the phenyl groups in the Cu(i) cluster through guest-host π-π interaction, which is quite unique when compared to the known acid-base neutralization and framework flexibility adjustment mechanisms. Such luminescence CO(2) sensing shows advantages like ultrafast response and good reversibility. Additionally, CuIDPO-loaded membranes were fabricated for spatially resolved 2D visual detection.

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