Synlett 2022; 33(03): 247-258
DOI: 10.1055/s-0041-1737792
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Tuning the Electrochemical and Photophysical Properties of Osmium-Based Photoredox Catalysts

Authors

  • Samantha L. Goldschmid

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA
  • Eva Bednářová

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA
  • Logan R. Beck

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA
  • Katherine Xie

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA
  • Nicholas E. S. Tay

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA
  • Benjamin D. Ravetz

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA
  • Jun Li

    b   Chemical Process Development, Bristol Myers Squibb, New Brunswick, New Jersey 08903, USA
  • Candice L. Joe

    b   Chemical Process Development, Bristol Myers Squibb, New Brunswick, New Jersey 08903, USA
  • Tomislav Rovis

    a   Department of Chemistry, Columbia University, New York, New York 10027, USA

E.B. acknowledges the Experientia Foundation for a postdoctoral fellowship. We are grateful to Bristol-Myers Squibb for support.


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Abstract

The use of low-energy deep-red (DR) and near-infrared (NIR) light to excite chromophores enables catalysis to ensue across barriers such as materials and tissues. Herein, we report the detailed photophysical characterization of a library of OsII polypyridyl photosensitizers that absorb low-energy light. By tuning ligand scaffold and electron density, we access a range of synthetically useful excited state energies and redox potentials.

1 Introduction

1.1 Scope

1.2 Measuring Ground-State Redox Potentials

1.3 Measuring Photophysical Properties

1.4 Synthesis of Osmium Complexes

2 Properties of Osmium Complexes

2.1 Redox Potentials of Os(L)2-Type Complexes

2.2 Redox Potentials of Os(L)3-Type Complexes

2.3 UV/Vis Absorption and Emission Spectroscopy

3 Conclusions

Supporting Information



Publication History

Received: 16 November 2021

Accepted after revision: 29 December 2021

Article published online:
14 January 2022

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