Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 13, Issue 36, Pages 42880-42888Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.1c12363
Keywords
electride; photoreducing agent; Pt(II) complex; electron transfer; radical generation
Funding
- Creative Materials Discovery Program [NRF-2015M3D1A1070639]
- Midcareer Research Program [NRF-2019R1A2C2003969]
- Institute for Basic Science [IBS-R011-D1]
- National Research Foundation - Ministry of Science, Information, and Communication Technology and Future Planning of Korea [NRF-2019R1A4A1029052]
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The research demonstrates an efficient reductive transformation strategy by combining a stable [Gd2C](2+)•2e(-) electride electron donor with cyclometalated Pt(II) complex photocatalysts. By releasing electrons in a specific solvent and utilizing localized anionic electrons in the interlayer space, persistent electron donation is achieved.
Electrides, which have excess anionic electrons, are solid-state sources of solvated electrons that can be used as powerful reducing agents for organic syntheses. However, the abrupt decomposition of electrides in organic solvents makes controlling the transfer inefficient, thereby limiting the utilization of their superior electron-donating ability. Here, we demonstrate the efficient reductive transformation strategy which combines the stable two-dimensional [Gd2C](2+)center dot 2e(-) electride electron donor and cyclometalated Pt(II) complex photocatalysts. Strongly localized anionic electrons at the interlayer space in the [Gd2C](2+)center dot 2e(-) electride are released via moderate alcoholysis in 2,2,2-trifluoroethanol, enabling persistent electron donation. The Pt(II) complexes are adsorbed onto the surface of the [Gd2C](2+)center dot 2e(-) electride and rapidly capture the released electrons at a rate of 10(7) s(-1) upon photoexcitation. The one-electron-reduced Pt complex is electrochemically stable enough to deliver the electron to substrates in the bulk, which completes the photoredox cycle. The key benefit of this system is the suppression of undesirable charge recombination because back electron transfer is prohibited due to the irreversible disruption of the electride after the electron transfer. These desirable properties collectively serve as the photoredox catalysis principle for the reductive generation of the benzyl radical from benzyl halide, which is the key intermediate for dehalogenated or homocoupled products.
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