Near‐Infrared Light‐Driven Photoredox Catalysis by Transition‐Metal‐Complex Nanodots

• Published in: Angewandte Chemie International Edition Vol. 61; no. 39; pp. e202204561 - n/a
• Main Authors: Wang, Lele, Sa, Rongjian, Wei, Yingcong, Ma, Xiongfeng, Lu, Chenggang, Huang, Haowei, Fron, Eduard, Liu, Ming, Wang, Wei, Huang, Shuping, Hofkens, Johan, Roeffaers, Maarten B. J., Wang, Yan‐jie, Wang, Junhui, Long, Jinlin, Fu, Xianzhi, Yuan, Rusheng
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 26.09.2022
• Edition: International ed. in English
• Subjects: Absorption; Carbonylation; Carbonyls; Catalysis; Copper; Dehydrogenation; Energy; Energy conversion; Energy harvesting; Full-Spectrum-Light Response; Iron; Molecules Aggregation; Nanodots; Near infrared radiation; Photons; Photoredox catalysis; Salts; Solar energy; Solar energy conversion; Spectral sensitivity; Transition Metal Complexes
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202204561

Developing light‐harvesting materials with broad spectral response is of fundamental importance in full‐spectrum solar energy conversion. We found that, when a series of earth‐abundant metal (Cu, Co, Ni and Fe) salts are dissolved in coordinating solvents uniformly dispersed nanodots (NDs) are formed rather than fully dissolving as molecular species. The previously unrecognized formation of this condensed state is ascribed to spontaneous aggregation of molecular transition‐metal‐complexes (TMCs) via weak intermolecular interactions, which results in redshifted and broadened absorption into the NIR region (200–1100 nm). Typical photoredox reactions, such as carbonylation and oxidative dehydrogenation, well demonstrate the feasibility of efficient utilization of NIR light (λ>780 nm) by TMCs NDs. Our finding provides a conceptually new strategy for extending the absorption towards low energy photons in solar energy harvesting and conversion via photoredox transformations. Aggregation of transition metal complexes (TMCs) into nanodots generates redshifted and broadened absorption covering the visible and the near‐infrared (NIR) region compared with the individual molecular complexes. The TMC nanodots demonstrate excellent performance for the carbonylation reaction under solar‐light illumination.