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 language | English |
|---|---|
| Pages (from-to) | 542-554 |
| Number of pages | 13 |
| Journal | Photochemical and Photobiological Sciences |
| Volume | 2 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - May 2003 |
Fingerprint
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 journal › Article
}
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 -