A spectroscopic and computationally minimal approach to the analysis of charge-transfer processes in conformationally fluxional mixed-valence and heterobimetallic complexes

Simon Gückel, Josef B.G. Gluyas, Samantha G. Eaves, Parvin Safari, Dmitry S. Yufit, Alexandre N. Sobolev, Martin Kaupp, Paul J. Low

Research output: Contribution to journalArticle

Abstract

Class II mixed-valence bimetallic complexes {[Cp′(PP)M]C≡C−C≡N[M′(PP)′Cp′]}2+ (M, M′=Ru, Fe; PP=dppe, (PPh3)2; Cp′=Cp*, Cp) exist as conformational ensembles in fluid solution, with a population of structures ranging from cis- to trans-like geometries. Each conformer gives rise to its own series of low-energy intervalence charge-transfer (IVCT) and local d–d transitions, which overlap in the NIR region, giving complex band envelopes in the NIR absorption spectrum, which prevent any meaningful attempt at analysis of the band shape. However, DFT and time-dependent (TD)DFT calculations with dispersion-corrected global-hybrid (BLYP35-D3) or local hybrid (lh-SsirPW92-D3) functionals on a small number of optimised structures chosen to sample the ground state potential energy hypersurfaces of each of these complexes has proven sufficient to explain the major features of the electronic spectra. Although modest in terms of computational expense, this approach provides a more accurate description of the underlying molecular electronic structure than would be possible through analysis of the IVCT band by using the static point-charge model of Marcus–Hush theory and derivatives, or TDDFT calculations from a single (global) minimum energy geometry.

Original languageEnglish
Pages (from-to)8837-8853
JournalChemistry - A European Journal
Volume25
Issue number37
Early online date2 May 2019
DOIs
Publication statusPublished - 2 Jul 2019

Fingerprint

Discrete Fourier transforms
Charge transfer
Molecular electronics
Geometry
Potential energy
Ground state
Molecular structure
Electronic structure
Absorption spectra
Derivatives
Fluids

Cite this

@article{7dfad8bfea6d407bb807c358dc6f53cc,
title = "A spectroscopic and computationally minimal approach to the analysis of charge-transfer processes in conformationally fluxional mixed-valence and heterobimetallic complexes",
abstract = "Class II mixed-valence bimetallic complexes {[Cp′(PP)M]C≡C−C≡N[M′(PP)′Cp′]}2+ (M, M′=Ru, Fe; PP=dppe, (PPh3)2; Cp′=Cp*, Cp) exist as conformational ensembles in fluid solution, with a population of structures ranging from cis- to trans-like geometries. Each conformer gives rise to its own series of low-energy intervalence charge-transfer (IVCT) and local d–d transitions, which overlap in the NIR region, giving complex band envelopes in the NIR absorption spectrum, which prevent any meaningful attempt at analysis of the band shape. However, DFT and time-dependent (TD)DFT calculations with dispersion-corrected global-hybrid (BLYP35-D3) or local hybrid (lh-SsirPW92-D3) functionals on a small number of optimised structures chosen to sample the ground state potential energy hypersurfaces of each of these complexes has proven sufficient to explain the major features of the electronic spectra. Although modest in terms of computational expense, this approach provides a more accurate description of the underlying molecular electronic structure than would be possible through analysis of the IVCT band by using the static point-charge model of Marcus–Hush theory and derivatives, or TDDFT calculations from a single (global) minimum energy geometry.",
keywords = "density functional theory, intervalence charge transfer, mixed valence, organometallic complexes, spectroelectrochemistry",
author = "Simon G{\"u}ckel and Gluyas, {Josef B.G.} and Eaves, {Samantha G.} and Parvin Safari and Yufit, {Dmitry S.} and Sobolev, {Alexandre N.} and Martin Kaupp and Low, {Paul J.}",
year = "2019",
month = "7",
day = "2",
doi = "10.1002/chem.201901200",
language = "English",
volume = "25",
pages = "8837--8853",
journal = "CHEMISTRY-A EUROPEAN JOURNAL",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "37",

}

A spectroscopic and computationally minimal approach to the analysis of charge-transfer processes in conformationally fluxional mixed-valence and heterobimetallic complexes. / Gückel, Simon; Gluyas, Josef B.G.; Eaves, Samantha G.; Safari, Parvin; Yufit, Dmitry S.; Sobolev, Alexandre N.; Kaupp, Martin; Low, Paul J.

In: Chemistry - A European Journal, Vol. 25, No. 37, 02.07.2019, p. 8837-8853.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A spectroscopic and computationally minimal approach to the analysis of charge-transfer processes in conformationally fluxional mixed-valence and heterobimetallic complexes

AU - Gückel, Simon

AU - Gluyas, Josef B.G.

AU - Eaves, Samantha G.

AU - Safari, Parvin

AU - Yufit, Dmitry S.

AU - Sobolev, Alexandre N.

AU - Kaupp, Martin

AU - Low, Paul J.

PY - 2019/7/2

Y1 - 2019/7/2

N2 - Class II mixed-valence bimetallic complexes {[Cp′(PP)M]C≡C−C≡N[M′(PP)′Cp′]}2+ (M, M′=Ru, Fe; PP=dppe, (PPh3)2; Cp′=Cp*, Cp) exist as conformational ensembles in fluid solution, with a population of structures ranging from cis- to trans-like geometries. Each conformer gives rise to its own series of low-energy intervalence charge-transfer (IVCT) and local d–d transitions, which overlap in the NIR region, giving complex band envelopes in the NIR absorption spectrum, which prevent any meaningful attempt at analysis of the band shape. However, DFT and time-dependent (TD)DFT calculations with dispersion-corrected global-hybrid (BLYP35-D3) or local hybrid (lh-SsirPW92-D3) functionals on a small number of optimised structures chosen to sample the ground state potential energy hypersurfaces of each of these complexes has proven sufficient to explain the major features of the electronic spectra. Although modest in terms of computational expense, this approach provides a more accurate description of the underlying molecular electronic structure than would be possible through analysis of the IVCT band by using the static point-charge model of Marcus–Hush theory and derivatives, or TDDFT calculations from a single (global) minimum energy geometry.

AB - Class II mixed-valence bimetallic complexes {[Cp′(PP)M]C≡C−C≡N[M′(PP)′Cp′]}2+ (M, M′=Ru, Fe; PP=dppe, (PPh3)2; Cp′=Cp*, Cp) exist as conformational ensembles in fluid solution, with a population of structures ranging from cis- to trans-like geometries. Each conformer gives rise to its own series of low-energy intervalence charge-transfer (IVCT) and local d–d transitions, which overlap in the NIR region, giving complex band envelopes in the NIR absorption spectrum, which prevent any meaningful attempt at analysis of the band shape. However, DFT and time-dependent (TD)DFT calculations with dispersion-corrected global-hybrid (BLYP35-D3) or local hybrid (lh-SsirPW92-D3) functionals on a small number of optimised structures chosen to sample the ground state potential energy hypersurfaces of each of these complexes has proven sufficient to explain the major features of the electronic spectra. Although modest in terms of computational expense, this approach provides a more accurate description of the underlying molecular electronic structure than would be possible through analysis of the IVCT band by using the static point-charge model of Marcus–Hush theory and derivatives, or TDDFT calculations from a single (global) minimum energy geometry.

KW - density functional theory

KW - intervalence charge transfer

KW - mixed valence

KW - organometallic complexes

KW - spectroelectrochemistry

UR - http://www.scopus.com/inward/record.url?scp=85067010667&partnerID=8YFLogxK

U2 - 10.1002/chem.201901200

DO - 10.1002/chem.201901200

M3 - Article

VL - 25

SP - 8837

EP - 8853

JO - CHEMISTRY-A EUROPEAN JOURNAL

JF - CHEMISTRY-A EUROPEAN JOURNAL

SN - 0947-6539

IS - 37

ER -