Boosting CO<sub>2</sub> photoreduction by π-π-induced preassembly between a Cu(I) sensitizer and a pyrene-appended Co(II) catalyst.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 36943881.
- Also identified by DOI 10.1073/pnas.2221219120 and PMC identifier 10068849.
- Licence recorded as CC BY-NC-ND.
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Abstract
The design of a highly efficient system for CO<sub>2</sub> photoreduction fully based on earth-abundant elements presents a challenge, which may be overcome by installing suitable interactions between photosensitizer and catalyst to expedite the intermolecular electron transfer. Herein, we have designed a pyrene-decorated Cu(I) complex with a rare dual emission behavior, aiming at additional π-interaction with a pyrene-appended Co(II) catalyst for visible light-driven CO<sub>2</sub>-to-CO conversion. The results of <sup>1</sup>H NMR titration, time-resolved fluorescence/absorption spectroscopies, quantum chemical simulations, and photocatalytic experiments clearly demonstrate that the dynamic π-π interaction between sensitizer and catalyst is highly advantageous in photocatalysis by accelerating the intermolecular electron transfer rate up to 6.9 × 10<sup>5</sup> s<sup>-1</sup>, thus achieving a notable apparent quantum yield of 19% at 425 nm with near-unity selectivity. While comparable to most earth-abundant molecular systems, this value is over three times of the pyrene-free system (6.0%) and far surpassing the benchmarking Ru(II) tris(bipyridine) (0.3%) and Ir(III) tris(2-phenylpyridine) (1.4%) photosensitizers under parallel conditions.