The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: A comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

Joanne Dyer, Werner J. Blau, Colin G. Coates, Caitriona M. Creely, John D. Gavey, Michael W. George, David Grills, Sarah Hudson, John M. Kelly, Pavel Matousek, John J. McGarvey, Jonathan McMaster, Anthony W. Parker, Michael Towrie, Julia A. Weinstein

Research output: Contribution to journalArticle

87 Citations (Scopus)

Abstract

The photophysical properties of fac-[Re(CO)3(dppz)(py)] + (1, where dppz = dipyrido[3,2-a:2′,3′-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3π→π*(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3π→π*(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3dπ(Re) →π*(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.

Original languageEnglish
Pages (from-to)542-554
Number of pages13
JournalPhotochemical and Photobiological Sciences
Volume2
Issue number5
DOIs
Publication statusPublished - May 2003

Fingerprint

Photolysis
Carbon Monoxide
flash
photolysis
Theoretical Models
Ligands
Infrared radiation
ligands
Phenanthrolines
Interleukin-3
Excited states
excitation
Raman Spectrum Analysis
Photoexcitation
photoexcitation
electronics
Density functional theory
Raman spectroscopy
Charge transfer
Metals

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Cell Biology
  • Biochemistry, Genetics and Molecular Biology(all)
  • Biochemistry
  • Biophysics

Cite this

The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN : A comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study. / Dyer, Joanne; Blau, Werner J.; Coates, Colin G.; Creely, Caitriona M.; Gavey, John D.; George, Michael W.; Grills, David; Hudson, Sarah; Kelly, John M.; Matousek, Pavel; McGarvey, John J.; McMaster, Jonathan; Parker, Anthony W.; Towrie, Michael; Weinstein, Julia A.

In: Photochemical and Photobiological Sciences, Vol. 2, No. 5, 05.2003, p. 542-554.

Research output: Contribution to journalArticle

Dyer, J, Blau, WJ, Coates, CG, Creely, CM, Gavey, JD, George, MW, Grills, D, Hudson, S, Kelly, JM, Matousek, P, McGarvey, JJ, McMaster, J, Parker, AW, Towrie, M & Weinstein, JA 2003, 'The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: A comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study', Photochemical and Photobiological Sciences, vol. 2, no. 5, pp. 542-554. https://doi.org/10.1039/b212628a
Dyer, Joanne ; Blau, Werner J. ; Coates, Colin G. ; Creely, Caitriona M. ; Gavey, John D. ; George, Michael W. ; Grills, David ; Hudson, Sarah ; Kelly, John M. ; Matousek, Pavel ; McGarvey, John J. ; McMaster, Jonathan ; Parker, Anthony W. ; Towrie, Michael ; Weinstein, Julia A. / The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN : A comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study. In: Photochemical and Photobiological Sciences. 2003 ; Vol. 2, No. 5. pp. 542-554.
@article{e35586ffa9b04ca4b529312d150caba3,
title = "The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN: A comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study",
abstract = "The photophysical properties of fac-[Re(CO)3(dppz)(py)] + (1, where dppz = dipyrido[3,2-a:2′,3′-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3π→π*(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3π→π*(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3dπ(Re) →π*(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.",
author = "Joanne Dyer and Blau, {Werner J.} and Coates, {Colin G.} and Creely, {Caitriona M.} and Gavey, {John D.} and George, {Michael W.} and David Grills and Sarah Hudson and Kelly, {John M.} and Pavel Matousek and McGarvey, {John J.} and Jonathan McMaster and Parker, {Anthony W.} and Michael Towrie and Weinstein, {Julia A.}",
year = "2003",
month = "5",
doi = "10.1039/b212628a",
language = "English",
volume = "2",
pages = "542--554",
journal = "Photochemical and Photobiological Sciences",
issn = "1474-905X",
publisher = "Royal Society of Chemistry",
number = "5",

}

TY - JOUR

T1 - The photophysics of fac-[Re(CO)3(dppz)(py)]+ in CH3CN

T2 - A comparative picosecond flash photolysis, transient infrared, transient resonance Raman and density functional theoretical study

AU - Dyer, Joanne

AU - Blau, Werner J.

AU - Coates, Colin G.

AU - Creely, Caitriona M.

AU - Gavey, John D.

AU - George, Michael W.

AU - Grills, David

AU - Hudson, Sarah

AU - Kelly, John M.

AU - Matousek, Pavel

AU - McGarvey, John J.

AU - McMaster, Jonathan

AU - Parker, Anthony W.

AU - Towrie, Michael

AU - Weinstein, Julia A.

PY - 2003/5

Y1 - 2003/5

N2 - The photophysical properties of fac-[Re(CO)3(dppz)(py)] + (1, where dppz = dipyrido[3,2-a:2′,3′-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3π→π*(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3π→π*(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3dπ(Re) →π*(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.

AB - The photophysical properties of fac-[Re(CO)3(dppz)(py)] + (1, where dppz = dipyrido[3,2-a:2′,3′-c]phenazine) in CH3CN have been investigated using a series of complementary techniques including visible and infrared transient absorption and resonance Raman spectroscopy on the picosecond and nanosecond timescales. The results confirm previous reports that the lowest-lying emissive state in 1 is a triplet intra-ligand (3IL) state localised on the dppz ligand and have provided detailed information on the dynamics of 1 upon photoexcitation, including the relative energies of the excited state species encountered and the electronic distribution within these. If the dppz ligand is viewed in terms of phenanthroline (phen) and phenazine (phz) moieties, the emissive state is probably more accurately described as a 3π→π*(phz) IL state. The picosecond studies have shown that this emissive state is formed, at least in part, within 30 ps of excitation from a precursor, which is possibly a 3π→π*(phen) IL state. On the nanosecond timescale, TRIR has been employed to elucidate further dynamics and reveal the presence of an energetically close-lying state in equilibrium with the emissive state. This has tentatively been assigned as being 3dπ(Re) →π*(phz) metal-to-ligand charge transfer (MLCT) in nature. A summary of the photophysics is proposed in the form of a Jablonski scheme. Time dependent density functional theory (TD-DFT) calculations support the relative ordering and suggested electronic character of the excited state species involved.

UR - http://www.scopus.com/inward/record.url?scp=0242611762&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0242611762&partnerID=8YFLogxK

U2 - 10.1039/b212628a

DO - 10.1039/b212628a

M3 - Article

C2 - 12803077

AN - SCOPUS:0242611762

VL - 2

SP - 542

EP - 554

JO - Photochemical and Photobiological Sciences

JF - Photochemical and Photobiological Sciences

SN - 1474-905X

IS - 5

ER -