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Oxidative two-state photoreactivity of a manganese(IV) complex using near-infrared light

Nature Chemistry (2024)Cite this article

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Abstract

Highly reducing or oxidizing photocatalysts are a fundamental challenge in photochemistry. Only a few transition metal complexes with Earth-abundant metal ions have so far advanced to excited state oxidants. All these photocatalysts require high-energy light for excitation, and their oxidizing power has not been fully exploited due to energy dissipation before reaching the photoactive state. Here we demonstrate that the complex [Mn(dgpy)2]4+, based on Earth-abundant manganese and the tridentate 2,6-diguanidylpyridine ligand (dgpy), evolves to a luminescent doublet ligand-to-metal charge transfer (2LMCT) excited state (1,435 nm, 0.86 eV) with a lifetime of 1.6 ns after excitation with low-energy near-infrared light. This 2LMCT state oxidizes naphthalene to its radical cation. Substrates with extremely high oxidation potentials up to 2.4 V enable the [Mn(dgpy)2]4+ photoreduction via a high-energy quartet 4LMCT excited state with a lifetime of 0.78 ps, proceeding via static quenching by the solvent. This process minimizes free energy losses and harnesses the full photooxidizing power, and thus allows oxidation of nitriles and benzene using Earth-abundant elements and low-energy light.

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Fig. 1: Steady-state UV/visible/near-infrared absorption and emission spectroscopy of [Mn(dgpy)2][PF6]4.
Fig. 2: Femtosecond TA investigations of [Mn(dgpy)2][PF6]4 in Ar-saturated CH3CN revealing the initial formation of the 4LMCT state followed by the slow ISC to the 2LMCT state.
Fig. 3: Quantum chemical calculations of excited states of [Mn(dgpy)2]4+ and the products of the photoinduced electron transfer reaction.
Fig. 4: Jablonski diagram and electron configurations of the involved excited states and redox states.

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Data availability

All data generated or analysed during this study are included in this published Article or its Supplementary Information files, which include irradiations under various conditions (light sources, substrates), luminescence and TA spectroscopic data and conductivity data. Raw data for the figures and supplementary figures and Cartesian coordinates for the optimized structures are also available from Figshare (https://doi.org/10.6084/m9.figshare.24886530). Source data are provided with this paper.

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Acknowledgements

This work was supported by the Max Planck Graduate Center with the Johannes Gutenberg University Mainz (MPGC). N.R.E. is a recipient of a position through the DFG Excellence Initiative by the Graduate School Materials Science in Mainz (GSC 266). This work was further supported by the Deutsche Forschungsgemeinschaft through grant INST 247/1018-1 FUGG to K.H. Parts of this research were conducted using the supercomputer Mogon and advisory services offered by Johannes Gutenberg University Mainz (http://www.hpc.uni-mainz.de) and the supercomputer Elwetritsch and advisory services offered by the Rheinland-Pfälzische Technische Universität Kaiserslautern-Landau (https://hpc.rz.rptu.de), which are members of the Allianz für Hochleistungsrechnen Rheinland-Pfalz (AHRP) and the Gauss Alliance e.V. We thank D. Zorn for performing the HPLC analyses. The funders had no role in study design, data collection and analysis, decision to publish or preparation of the paper.

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Authors and Affiliations

  1. Department of Chemistry, Johannes Gutenberg University, Mainz, Germany

    Nathan R. East, Robert Naumann, Christoph Förster, Gregor Diezemann & Katja Heinze

  2. Department of Physics and Astronomy, Vrije Universiteit Amsterdam, Amsterdam, the Netherlands

    Charusheela Ramanan

  3. Max-Planck-Institute for Polymer Research, Mainz, Germany

    Charusheela Ramanan

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  1. Nathan R. East
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N.R.E. performed the syntheses, the reactivity studies, the irradiation experiments and the computational studies. R.N. performed and analysed the luminescence and ultrafast time-resolved experiments and provided data interpretation. C.F. performed and assisted with the computational studies. C.R. assisted with the time-resolved experiments. G.D. performed and analysed the molecular dynamics simulations. K.H. conceptualized the research, conceived the experiments and performed data analyses and interpretation. All authors discussed the results and commented on the paper.

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Correspondence to Katja Heinze.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–57 and Tables 1 and 2.

Supplementary Data 1

Source data of Supplementary Figs. 1–57.

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Source Data Fig. 1

Absorption and emission spectra of [Mn(dgpy)2]4+ and photooxidation of naphthalene.

Source Data Fig. 2

TA spectra of [Mn(dgpy)2]4+ in MeCN and time-dependent DFT transitions of the doublet.

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East, N.R., Naumann, R., Förster, C. et al. Oxidative two-state photoreactivity of a manganese(IV) complex using near-infrared light. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01446-8

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