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Abstract Conventional organic photocatalysis typically relies on ultraviolet and short‐wavelength visible photons as the energy source. However, this approach often suffers from competing light absorption by reactants, products, intermediates, and co‐catalysts, leading to reduced quantum efficiency and side reactions. To address this issue, we developed novel organic two‐photon‐absorbing (TPA) photosensitizers capable of functioning under deep red and near‐infrared light irradiation. Three model reactions including cyclization, Sonogashira Csp2−Cspcross‐coupling, and Csp2−N cross‐coupling reactions were selected to compare the performance of the new photosensitizers under both blue (427 nm) and deep red (660 nm) light irradiation. The obtained results unambiguously prove that for reactions involving blue light‐absorbing reactants, products, and/or co‐catalysts, deep red light source resulted in better performance than blue light when utilizing our TPA photosensitizers. This work highlights the potential of our metal‐free TPA photosensitizers as a sustainable and effective solution to mitigate the competing light absorption issue in photocatalysis, not only expanding the scope of organic photocatalysts but also reducing reliance on expensive Ru/Ir/Os‐based photosensitizers.
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Two-photon-absorbing ruthenium complexes enable near infrared light-driven photocatalysis
Abstract One-photon-absorbing photosensitizers are commonly used in homogeneous photocatalysis which require the absorption of ultraviolet (UV) /visible light to populate the desired excited states with adequate energy and lifetime. Nevertheless, the limited penetration depth and competing absorption by organic substrates of UV/visible light calls upon exploring the utilization of longer-wavelength irradiation, such as near-infrared light (λ irr > 700 nm). Despite being found applications in photodynamic therapy and bioimaging, two-photon absorption (TPA), the simultaneous absorption of two photons by one molecule, has been rarely explored in homogeneous photocatalysis. Herein, we report a group of ruthenium polypyridyl complexes possessing TPA capability that can drive a variety of organic transformations upon irradiation with 740 nm light. We demonstrate that these TPA ruthenium complexes can operate in an analogous manner as one-photon-absorbing photosensitizers for both energy-transfer and photoredox reactions, as well as function in concert with a transition metal co-catalyst for metallaphotoredox C–C coupling reactions.
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- PAR ID:
- 10332335
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s41467-022-29981-3
