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Low-spin cobalt(ii) redox shuttle by isocyanide coordination

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Abstract

Coordination of the strong-field ligand 2,6-dimethylphenyl isocyanide (DMP-CN) to the Co(PY5Me2) framework, where PY5Me2 represents the pentadentate ligand 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine, has resulted in a new low-spin Co(II) complex with a relatively low reorganization energy and fast electron-transfer kinetics compared to the prototypical cobalt tris-bipyridine redox shuttle, [Co(bpy)3]3+/2+, where bpy represents 2,2′-bipyridine. Despite nearly 160 mV reduced regeneration driving force, the [Co(PY5Me2)(DMP-CN)]3+/2+ redox shuttle displayed an increased regeneration efficiency relative to [Co(bpy)3]3+/2+, however recombination losses hinder the performance as evidenced by a reduced recombination resistance. Future directions point to low-spin Co(II) redox shuttles with more negative redox potentials to be paired with a dye or dye mixture that absorbs into the near infrared region.

Graphical abstract: Low-spin cobalt(ii) redox shuttle by isocyanide coordination

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Article information


Submitted
26 Feb 2020
Accepted
07 Mar 2020
First published
09 Mar 2020

Sustainable Energy Fuels, 2020, Advance Article
Article type
Paper

Low-spin cobalt(II) redox shuttle by isocyanide coordination

A. L. Raithel, T. Kim, K. C. Nielsen, R. J. Staples and T. W. Hamann, Sustainable Energy Fuels, 2020, Advance Article , DOI: 10.1039/D0SE00314J

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