Step-scan FTIR absorption difference time-resolved spectroscopy studies the excited state electronic structures and decay kinetics of d[sup 6] transition metal polypyridine complexes

1998 ◽  
Author(s):  
G. D. Smith ◽  
B. M. Paegel ◽  
R. A. Palmer ◽  
P. Chen ◽  
K. M. Omberg ◽  
...  

1999 ◽  
Vol 19 (1-4) ◽  
pp. 291-298 ◽  
Author(s):  
Gregory D. Smith ◽  
Pingyun Chen ◽  
James L. Chao ◽  
Kristin M. Omberg ◽  
Darius A. Kavaliunas ◽  
...  

Step-scan Fourier transform absorption difference time-resolved spectroscopy (S2FTIR ∆A TRS) has been used to collect mid-IR time-resolved infrared spectra of the transient electronic excited states of polypyridine transition metal complexes with 10 ns time resolution. The time-resolved data can be used for kinetic analysis or to generate “snapshots” of the lowest lying excited state. Shifts of vibrational bands in the excited state relative to the ground state can be used to infer significant details of the electronic structure of the excited state. The multiplex advantage of the FTIR technique allows a wide variety of vibrational bands to be analyzed for this purpose. In the example illustrated, the shift of the ester ν(CO) band in {Ru(bpy)[4,4′-(COOEt)2bpy]2}2+ compared to those in related complexes has been used to address the question of electron delocalization in the excited state.





Author(s):  
Paloma Lizondo-Aranda ◽  
Lara Martínez-Fernández ◽  
Miguel A. Miranda ◽  
Roberto Improta ◽  
Thomas Gustavsson ◽  
...  


2005 ◽  
Vol 44 (15) ◽  
pp. 5530-5536 ◽  
Author(s):  
Brendan P. Macpherson ◽  
Paul V. Bernhardt ◽  
Andreas Hauser ◽  
Stéphane Pagès ◽  
Eric Vauthey


2008 ◽  
Vol 352 (1-3) ◽  
pp. 97-105 ◽  
Author(s):  
Lazaro A. Padilha ◽  
Scott Webster ◽  
Honghua Hu ◽  
Olga V. Przhonska ◽  
David J. Hagan ◽  
...  


1997 ◽  
Vol 51 (4) ◽  
pp. 580-583 ◽  
Author(s):  
Pingyun Chen ◽  
Richard A. Palmer

Ten-nanosecond time resolution has been achieved with step-scan FT-IR absorbance difference spectroscopy (S2FT-IR Δ A TRS) and demonstrated by measuring Δ A spectra of fac-[Re(bpy)(CO)3Cl] and cis-[Os(bpy)2(CO)(4,4′-bpy)]2+ (bpy = 2,2′-bipyridine; 4,4′-bpy=4,4′-bipyridine) in CH3CN solution, following 355-nm laser excitation. In both complexes, the large shifts in (CO) to higher energy are consistent with the assignment that the lowest-energy excited states are metal-to-ligand charge transfer in nature. For [Os(bpy)2(CO)(4,4′-bpy)]2+, it is also possible to measure the excited-state decay kinetics, again with 10-ns resolution. In addition, Δ A bands are observed that are related to excited-state vibrations of the bipyridine ligands. Δ A spectra of good signal-to-noise ratio can be obtained for complexes with lifetimes as short as 10 ns.



2004 ◽  
Vol 69 (4) ◽  
pp. 748-758 ◽  
Author(s):  
Israel V. Muthu Vijayan Enoch ◽  
Meenakshisundaram Swaminathan

The photophysical and photoprototropic behaviour of 4-aminobiphenyl (4ABP) in aqueous β-cyclodextrin (β-CDx) solution has been investigated using steady-state and time-resolved fluorescence spectroscopy. Fluorescence of the neutral form of 4ABP is enhanced due to the formation of a 1:1 complex with β-CDx. The formation of this complex has been confirmed by time-resolved spectroscopy. In the presence of β-CDx, no change was observed in the ground state pKa value but the excited state pKa value changed. Based on its photophysical and photoprototropic characteristics in β-CDx, the structure of the 1:1 inclusion complex is proposed.





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