Probing intraligand and charge transfer excited states of fac-[Re(R)(CO)3(CO2Et-dppz)]+ (R = py, 4-Me2N-py; CO2Et-dppz = dipyrido[3,2a:2′,3′c]phenazine-11-carboxylic ethyl ester) using time-resolved infrared spectroscopy

2007 ◽  
Vol 6 (11) ◽  
pp. 1158 ◽  
Author(s):  
Marina K. Kuimova ◽  
Xue Zhong Sun ◽  
Pavel Matousek ◽  
David C. Grills ◽  
Anthony W. Parker ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Charge Transfer ◽  
Ethyl Ester ◽  
Excited States ◽  
Time Resolved ◽  
Time Resolved Infrared Spectroscopy

scholarly journals Excited States and Intermediates by Time-Resolved Infrared Spectroscopy

1999 ◽  
Vol 19 (1-4) ◽  
pp. 245-251 ◽  
Author(s):  
J. J. Turner ◽  
M. W. George ◽  
I. P. Clark ◽  
I. G. Virrels
Keyword(s):  
Infrared Spectroscopy ◽  
Excited State ◽  
Charge Transfer ◽  
Excited States ◽  
Fast Time ◽  
Time Resolved ◽  
Excited Species ◽  
Charge Transfer Transitions ◽  
Time Resolved Infrared Spectroscopy ◽  
Kinetics Of

For coordination compounds containing CO or CN groups, fast time-resolved infrared spectroscopy (TRIR) provides a convenient method of probing excited states and intermediates. TRIR has proved particularly powerful for probing the structure and kinetics of organometallic intermediates. The interpretation is particularly straightforward when combined with IR data from matrix isolation experiments, although there can be some subtle differences. In excited state studies, shifts in ν(CO) and ν(CN) frequencies, from ground to excited state, are sensitive to the changes in electron distribution on excitation, thus allowing the distinction between charge-transfer and non-charge-transfer transitions. Subtle effects on excited state ν(CO) band positions occur with change from fluid to rigid solvent-“infrared rigidochromism”. There is often a change in ν(CO) band width on excitation; this can be interpreted in terms of specific interactions between the excited species and the solvent. This paper presents some of our recent work in this area.

Application of Time-Resolved Infrared Spectroscopy to Electronic Structure in Metal-to-Ligand Charge-Transfer Excited States

2002 ◽  
Vol 41 (23) ◽  
pp. 6071-6079 ◽  
Author(s):  
Dana M. Dattelbaum ◽  
Kristin M. Omberg ◽  
Jon R. Schoonover ◽  
Richard L. Martin ◽  
Thomas J. Meyer
Keyword(s):  
Electronic Structure ◽  
Infrared Spectroscopy ◽  
Charge Transfer ◽  
Excited States ◽  
Time Resolved ◽  
Ligand Charge Transfer ◽  
Time Resolved Infrared Spectroscopy

scholarly journals Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

2016 ◽  
Vol 7 (5) ◽  
pp. 3075-3084 ◽  
Author(s):  
Fergus E. Poynton ◽  
James P. Hall ◽  
Páraic M. Keane ◽  
Christine Schwarz ◽  
Igor V. Sazanovich ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Excited States ◽  
Direct Observation ◽  
Time Resolved ◽  
Time Resolved Infrared Spectroscopy

Strikingly different TRIR spectra are recorded for the complex in D2O or CD3CN or when DNA-bound.

scholarly journals Ruthenium Assemblies for CO2 Reduction and H2 Generation: Time Resolved Infrared Spectroscopy, Spectroelectrochemistry and a Photocatalysis Study in Solution and on NiO

2021 ◽  
Vol 9 ◽  
Author(s):  
Florian J. R. Cerpentier ◽  
Joshua Karlsson ◽  
Ralte Lalrempuia ◽  
Michael P. Brandon ◽  
Igor V. Sazanovich ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Excited States ◽  
Co2 Reduction ◽  
Carbonyl Groups ◽  
Intermediate Species ◽  
Time Resolved ◽  
H2 Generation ◽  
Catalytic Metal ◽  
The One ◽  
Time Resolved Infrared Spectroscopy

Two novel supramolecular complexes RuRe ([Ru(dceb)2(bpt)Re(CO)3Cl](PF6)) and RuPt ([Ru(dceb)2(bpt)PtI(H2O)](PF6)2) [dceb = diethyl(2,2′-bipyridine)-4,4′-dicarboxylate, bpt = 3,5-di(pyridine-2-yl)-1,2,4-triazolate] were synthesized as new catalysts for photocatalytic CO2 reduction and H2 evolution, respectively. The influence of the catalytic metal for successful catalysis in solution and on a NiO semiconductor was examined. IR-active handles in the form of carbonyl groups on the peripheral ligand on the photosensitiser were used to study the excited states populated, as well as the one-electron reduced intermediate species using infrared and UV-Vis spectroelectrochemistry, and time resolved infrared spectroscopy. Inclusion of ethyl-ester moieties led to a reduction in the LUMO energies on the peripheral bipyridine ligand, resulting in localization of the 3MLCT excited state on these peripheral ligands following excitation. RuPt generated hydrogen in solution and when immobilized on NiO in a photoelectrochemical (PEC) cell. RuRe was inactive as a CO2 reduction catalyst in solution, and produced only trace amounts of CO when the photocatalyst was immobilized on NiO in a PEC cell saturated with CO2.

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