1994
DOI: 10.1021/ic00093a009
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Structural Investigation of the Ground and Excited States of ClRe(CO)3(4,4'-bipyridyl)2 using Vibrational Spectroscopy

Abstract: Fast time-resolved infrared spectroscopy (TRIR) is used to probe the v(CO) spectrum of ClRe(CO)3(4,4'-bipyridyl)2 in the lowest MLCT (metal-to-ligand charge transfer) excited state. The three ground-state v(CO) bands all shift up in frequency, but not by the same amount. The energy-factored force field (EFFF) of the ground state is accurately solved by employing ,3CO-enrichment. Approximate methods yield information on the force field of the excited state; the principal EFFF force constants (¿co(ami) and fcco(… Show more

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Cited by 136 publications
(148 citation statements)
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“…35 The transient absorption spectra were in both cases assigned to the 3 MLCT state, supported by the evidence from time-resolved Raman 11 and IR spectroscopies. 4,27,55 The two bands at 375 and 470 nm present in the transient spectra of all three X/bpy complexes can be attributed to the π 1 * f π 2 * and π f π 1 * IL transitions of the (bpy) ‚-chromophore present in the excited molecules, since they closely resemble the bands found in the absorption spectrum of reduced [bpy] ‚-generated independently. 56,57 Also the absorption spectrum of reduced [Re(Br)(CO) 3 (bpy′)] -, with the extra electron localized on the bpy′ ligand, possesses bands in this region with comparable shape and relative intensity.…”
Section: Resultsmentioning
confidence: 71%
“…35 The transient absorption spectra were in both cases assigned to the 3 MLCT state, supported by the evidence from time-resolved Raman 11 and IR spectroscopies. 4,27,55 The two bands at 375 and 470 nm present in the transient spectra of all three X/bpy complexes can be attributed to the π 1 * f π 2 * and π f π 1 * IL transitions of the (bpy) ‚-chromophore present in the excited molecules, since they closely resemble the bands found in the absorption spectrum of reduced [bpy] ‚-generated independently. 56,57 Also the absorption spectrum of reduced [Re(Br)(CO) 3 (bpy′)] -, with the extra electron localized on the bpy′ ligand, possesses bands in this region with comparable shape and relative intensity.…”
Section: Resultsmentioning
confidence: 71%
“…Observation of enhanced bands due to MeDpe + vibrations is compatible with both MLCT and IL characters of the resonant electronic transitions, while enhancement of the n(CO) band is diagnostic [7,42,[50][51][52][53] of Re(CO) 3 !MeDpe + MLCT. By combining information from UV/Vis and rR spectroscopy, we may conclude that the lowest near-UV absorption band is primarily due to an IL transition while the "tail" extending into the visible region originates in an MLCT transition from Re(Cl)(CO) 3 to MeDpe Figure 5) is qualitatively similar to that of [Re(Cl)(CO) 3 -…”
mentioning
confidence: 62%
“…The positive and negative spectral features correspond to the photogenerated transient and the depleted ground state population (bleach), respectively. Following excitation of [Re(Cl)(CO) 3 [50] to the A'(2), A'', and A'(1) n(CO) modes, respectively. The A'(1) n(CO) bleach intensity is smaller than expected from the ground state FTIR spectrum because of a strong overlap with a positive transient IR absorption.…”
Section: Spectrum Of [Rea C H T U N G T R E N N U N G (Medpe + )(Co) mentioning
confidence: 99%
“…Complexes [ReX(CO) 3 (P ∩O)] (1, X=Cl; 2, X=Br) were isolated as air-stable red-brown needles while complexes [ReX(CO) 3 (P ∩N] (3, X=Cl; 4, X=Br) were separated as yellowish blocks. In the rhenium(I) carbonyl stretching region of t he infrared spectra, the complexes show three strong peaks consistent with a facial arrangement o f t he three carbonyl groups [33,34], which are assigned as the A′ (1), A ″ and A′(2) vibrations, respectively [35]. The IR spectra of the rhenium(I) aldehyde phosphine complexes 1 and 2 show a single strong band at ca.…”
Section: Resultsmentioning
confidence: 92%