The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes

The ground and excited properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups have been investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituent allowed the effects on the photophysi...

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Main Authors: Adams, Bethany, Shillito, Georgina E., Salm, Holly van der, Horvath, Raphael, Larsen, Christopher B., Lucas, Nigel T., George, Michael W., Gordon, Keith C.
Format: Article
Published: American Chemical Society 2017
Online Access:https://eprints.nottingham.ac.uk/48548/
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author Adams, Bethany
Shillito, Georgina E.
Salm, Holly van der
Horvath, Raphael
Larsen, Christopher B.
Lucas, Nigel T.
George, Michael W.
Gordon, Keith C.
author_facet Adams, Bethany
Shillito, Georgina E.
Salm, Holly van der
Horvath, Raphael
Larsen, Christopher B.
Lucas, Nigel T.
George, Michael W.
Gordon, Keith C.
author_sort Adams, Bethany
building Nottingham Research Data Repository
collection Online Access
description The ground and excited properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups have been investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituent allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including TD-DFT, resonance Raman and time resolved infrared. The ground state optical properties show significant variation as a result of donor group modulation, with increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest energy transition, which was consistently ILCT in nature. However, across all complexes studied there was minimal perturbation to the excited state properties and dynamics. Three excited states on the picosecond, nanosecond and microsecond time scales were observed in all cases, corresponding to 1ILCT, ππ* and 3ILCT respectively.
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spelling nottingham-485482020-05-04T19:11:00Z https://eprints.nottingham.ac.uk/48548/ The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes Adams, Bethany Shillito, Georgina E. Salm, Holly van der Horvath, Raphael Larsen, Christopher B. Lucas, Nigel T. George, Michael W. Gordon, Keith C. The ground and excited properties of a series of [ReCl(CO)3(dppz)] complexes with substituted donor groups have been investigated. Alteration of donor-acceptor communication through modulation of torsional angle and the number and nature of the donor substituent allowed the effects on the photophysical properties to be characterized though both computational and spectroscopic techniques, including TD-DFT, resonance Raman and time resolved infrared. The ground state optical properties show significant variation as a result of donor group modulation, with increased angle between the donor and acceptor blue-shifting and depleting the intensity of the lowest energy transition, which was consistently ILCT in nature. However, across all complexes studied there was minimal perturbation to the excited state properties and dynamics. Three excited states on the picosecond, nanosecond and microsecond time scales were observed in all cases, corresponding to 1ILCT, ππ* and 3ILCT respectively. American Chemical Society 2017-10-06 Article PeerReviewed Adams, Bethany, Shillito, Georgina E., Salm, Holly van der, Horvath, Raphael, Larsen, Christopher B., Lucas, Nigel T., George, Michael W. and Gordon, Keith C. (2017) The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes. Inorganic Chemistry, 56 (21). pp. 12967-12977. ISSN 1520-510X http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01710 doi:10.1021/acs.inorgchem.7b01710 doi:10.1021/acs.inorgchem.7b01710
spellingShingle Adams, Bethany
Shillito, Georgina E.
Salm, Holly van der
Horvath, Raphael
Larsen, Christopher B.
Lucas, Nigel T.
George, Michael W.
Gordon, Keith C.
The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes
title The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes
title_full The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes
title_fullStr The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes
title_full_unstemmed The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes
title_short The alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted Re-dppz complexes
title_sort alteration of intra-ligand donor-acceptor interactions through torsional connectivity in substituted re-dppz complexes
url https://eprints.nottingham.ac.uk/48548/
https://eprints.nottingham.ac.uk/48548/
https://eprints.nottingham.ac.uk/48548/