Where's the spin? A DFT study of mixed-valence cyanide-bridged ruthenium polypyridines

Pieslinger GE, Cadranel A, Baraldo LM (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Journal of the Brazilian Chemical Society Sociedade Brasileira de Química, SBQ

Book Volume: 31

Pages Range: 2360-2370

Journal Issue: 11

DOI: 10.21577/0103-5053.20200135

Abstract

This article discusses the use of density functional theory (DFT) calculations in classifying and characterizing bimetallic ruthenium mixed-valence systems in terms of their electronic localization/ delocalization degree. A standard B3LYP/LanL2DZ methodology including integral equation formalism-polarizable continuum model (IEF-PCM) solvent model is evaluated for a set of 16 non-symmetric mixed-valence cyanide-bridged ruthenium polypyridines. This procedure reproduces well the features of the observed electronic and vibrational spectra, with better agreement for the more delocalized systems, and therefore provides an appropriate description of the electronic structures. Computed spin densities support class II or class III Robin-Day assignments and allow to quantify the electronic delocalization degree. The applied methodology yields good results due to the nature of the systems explored, which display a strong electronic coupling promoted by the cyanide-bridge and a lack of strong specific solvation effects. This procedure is not only useful in the study of ground state mixed-valence systems, but also provides a powerful insight into photoinduced mixed-valence excited states of related complexes.

Authors with CRIS profile

Alejandro Cadranel Lehrstuhl für Physikalische Chemie I

Additional Organisation(s)

Interdisziplinäres Zentrum für Molekulare Materialien

Involved external institutions

Universidad de Buenos Aires (UBA) / University of Buenos Aires AR Argentina (AR)

How to cite

APA:

Pieslinger, G.E., Cadranel, A., & Baraldo, L.M. (2020). Where's the spin? A DFT study of mixed-valence cyanide-bridged ruthenium polypyridines. Journal of the Brazilian Chemical Society, 31(11), 2360-2370. https://dx.doi.org/10.21577/0103-5053.20200135

MLA:

Pieslinger, German E., Alejandro Cadranel, and Luis M. Baraldo. "Where's the spin? A DFT study of mixed-valence cyanide-bridged ruthenium polypyridines." Journal of the Brazilian Chemical Society 31.11 (2020): 2360-2370.

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