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The ligand-to-metal charge transfer excited state of [Re(dmpe)3]2+


The ligand-to-metal charge transfer (LMCT) transitions of [Re(dmpe)3]2+ (dmpe = bis-1,2-(dimethylphosphino)ethane) were interrogated using UV/Vis absorbance spectroscopy, photoluminescence spectroscopy, and time-dependent density functional theory. The solvent dependence of the lowest energy charge transfer transition was quantified; no solvatochromism was observed. TD-DFT calculations reveal the dominant LMCT transition is highly symmetric and delocalized involving all phopshine ligand donors in the charge transfer, providing an understanding for the absence of solvatochromism of [Re(dmpe)3]2+.

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This material is based on work supported by the National Science Foundation under award number CHE-1954868 (synthesis, spectroscopy, and preliminary computations) and award number CHE-1554855 (computational studies). J.L.D. acknowledges support from a Packard Fellowship for Science and Engineering. T.M.R. acknowledges support from the National Science Foundation Graduate Research Fellowship Grant No. DGE-1650116. We thank the University of North Carolina’s Department of Chemistry NMR Core Laboratory for the use of their NMR spectrometers. We thank Cole Gruninger and Kelsey Brereton for fruitful discussions and guidance.

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Rodriguez, T.M., Deegbey, M., Jakubikova, E. et al. The ligand-to-metal charge transfer excited state of [Re(dmpe)3]2+. Photosynth Res (2021).

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  • Ligand-to-metal charge transfer
  • Photophysics
  • TD-DFT
  • Charge transfer
  • Rhenium