Near-Infrared-Responsive Single-Component Hybrid Lead Halides for Photocatalytic C2 Hydrocarbon Production from CO2

Hybrid lead halides have demonstrated significant promise for CO₂ photoreduction due to their excellent photophysical properties. However, developing a single-component hybrid lead halide that combines high intrinsic stability with near-infrared (NIR) absorption (accounting for over 50% of solar enrgy) remains a significant challenge. Herein, to address both issues, we design a series of nine ultra-stable lead halide frameworks functionalized by bis(terpyridine)-metal (M(tpy) ₂ , M = Fe ²⁺ /Co ²⁺ /Ni ²⁺ ) complexes, which exhibit strong light absorption extending into the NIR region up to 1150 nm. Unlike their symmetric chloride and bromide analogues, the charge-polarized Pb ₂ I ₄ (DMF) sites in lead iodide-M(tpy) ₂ frameworks serve as highly efficient C–C coupling centers for C ₂ production in NIR-driven CO ₂ photoreduction, achieving remarkable C ₂ production rates of up to 14.3 µ mol g ^− 1 h ^− 1 with electron selectivities as high as 86%. These performances substantially surpass all previously reported single-component NIR-responsive photocatalysts, highlighting the potential of coordination-driven assembly of ultra-stable lead halide frameworks for NIR-driven artificial photosynthesis.