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Single-chromophore single-molecule photocatalyst for the production of dihydrogen using low-energy light

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Abstract

Single-chromophore single-molecule photocatalysts for the conversion and storage of solar energy into chemical bonds are rare, inefficient and do not use significant portions of the visible spectrum. Here we show a new, air-stable bimetallic scaffold that acts as a single-chromophore photocatalyst for hydrogen-gas generation and operates with irradiation wavelengths that span the ultraviolet to the red/near-infrared. Irradiation in acidic solutions that contain an electron donor results in the catalytic production of hydrogen with 170 ± 5 turnovers in 24 hours and an initial rate of 28 turnovers per hour. The catalysis proceeds through two stepwise excited-state redox events—atypical of the currently known homogeneous photocatalysis—and features the storage of multiple redox equivalents on a dirhodium catalyst enabled by low-energy light.

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Fig. 1: Schematic representation of structures 1–3.
Fig. 2: Electronic absorption spectrum of 1.
Fig. 3: Hydrogen gas produced on the irradiation of complex 1 with red light over a period of 24 h.
Fig. 4: Mechanistic study of the reactivity of the catalytic intermediate, the one-electron reduced 1, [1]1−, in DMF in the presence of the electron donor BNAH (0.2 M).
Fig. 5: Proposed mechanism of the photocatalytic H2 production by 1.

Data availability

All the data supporting the findings of this study are available from the corresponding author upon reasonable request. Crystallographic data for structure 1 reported in this article has been deposited at the Cambridge Crystallographic Data Centre under deposition number CCDC 1871363. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

We thank the Support from the Department of Energy, Office of Science, Office of Basic Energy Sciences (DE-SC0020243) and The Ohio State University for partial support of this work and acknowledge A. Co for her invaluable insights regarding the electrochemical results, W. Kender for discussions on the mechanistic details and the Center for Chemical and Biophysical Dynamics (CCBD) for use of the ultrafast laser facility.

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Authors and Affiliations

Authors

Contributions

T.J.W. conceptualized the molecule, synthesized and characterized 1, performed investigations, which included the transient absorption and photocatalysis experiments, co-investigated the mechanistic model and drafted the manuscript. C.X. investigated the electrochemical properties and also performed photocatalysis experiments, co-investigated the mechanistic model and reviewed and edited the results, J.H. validated electronic absorption experiments and synthesized additional material of the target complex. J.C.G. collected the crystallographic data. C.T. supervised the project, aided in the experimental and mechanistic design, acquired funding and developed and edited the manuscript.

Corresponding author

Correspondence to C. Turro.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Methods and Supplementary data; Supplementary Tables 1–3 and Figs. 1–25.

Crystallographic data

CIF for 1; CCDC reference 1871363.

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Whittemore, T.J., Xue, C., Huang, J. et al. Single-chromophore single-molecule photocatalyst for the production of dihydrogen using low-energy light. Nat. Chem. 12, 180–185 (2020). https://doi.org/10.1038/s41557-019-0397-4

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