Sub-picosecond time-resolved intramolecular electronic energy transfer in bichromophoric rhodamine dyes in solution

Érnsting, N. P.; Kaschke, M.; Kleinschmidt, J.; Drexhage, K. H.; Huth, Volker

doi:10.1016/0301-0104(88)80024-7

Cited by 24 publications

(7 citation statements)

References 23 publications

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“…Inspection of these data reveals that the calculated (i.e., the solid line) electron-transfer rates for systems 5-8 are '-3 greater than the diffusion-controlled rate (/?Tln Xobs = (0.62-3.6) X 1010 M"1 s"1). This result suggests that reactions with driving forces more negative than systems [5][6][7][8] will possess sufficiently fast activated processes to ensure that the observed electron-transfer rate will reflect electron-exchange processes governed solely by diffusion (i.e., kaa » kD). The bipyridinium ion quenchers satisfy this criterion.…”

Section: Discussionmentioning

confidence: 99%

Contribution of long-range Coulomb interactions to bimolecular luminescence quenching reactions

Newsham¹,

Cukier²,

Nocera³

1991

J. Phys. Chem.

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9660J . Phys. Chem. 1991. 95, 9660-9666 flexible molecules. However, the resolution obtained from a single measurement can be modest (see xR2 surfaces for single files) and estimated values of the recovered parameters can be questionable. Beechem and H a d have recently discussed this problem for time-domain measurements and suggested simultaneous analysis of the donor and acceptor decay kinetics. This type of global analysis is potentially valuable and intuitively obvious, but is very difficult to realize in practice. Usually, acceptors are excited simultaneously during the excitation of the donor, and the amount of excited acceptor molecules due to energy transfer can be small compared with the whole population of excited-state acceptors. That is, the population or^ excited acceptors can be predominately the result of acceptors which are directly excited. The time-dependent decays of these acceptors do not contain any information on the distance distributions or dynamics, and this component can only result in decreased information content and/or resolution from the data. One must also separate donor and acceptor absorption and emission spectra and introduce additional parameters into the analysis to account for direct acceptor excitation and/or spectral overlap. I n contrast, the global analysis obtained by varying the donor lifetime does not introduce any additional parameters, gives an acceptable increase of the resolution for each fitted parameter, and can be used for any donor-acceptor system including nonfluorescent acceptors.The recovered initial distance distribution (Figure 9, insert, solid line) is in very good agreement with that found previously for TU2D in viscous solution32 (Figure 9, insert, dashed line). The diffusion coefficient, D = I .26 X cm2/s (I26 A2/ns), is in the range of expected values for small molecules in low-viscosity solutions. I t is interesting to compare the end-to-end diffusion coefficient with that obtained for a nonlinked system. Indoleto-dansyl intermolecular energy transfer has been investigated previously in propylene glycol and methanol.33 The data were fitted well to a Gosele et al. model" yielding a diffusion coefficient in methanol at 20 "C, D = 2.64 X cm2/s. The end-to-end diffusion coefficient obtained for TU2D in methanol is only twice smaller than that recovered from the mixture of indole and dansyl, where the polyethylene linker was not present. The data obtained for the TU2D donor-acceptor system and indole-dansyl mixture show that the polyethylene linker containing 22 carbons is highly flexible and has a moderate influence on end-to-end diffusion.The luminescence quenching of the hexanuclear cluster ions Mo,CI,,~-and W6II4'-by pyridinium and bipyridinium ions in nonaqueous solution has been investigated. Stern-Volmer (SV) plots of the emission intensity and lifetime quenching data for the reaction of M6X142-* with pyridinium acceptors are linear, and slopes of -0.48 for plots of R T In kobs vs the free energy driving force for electron transfer are in accordance...

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Section: Discussionmentioning

confidence: 99%

Contribution of long-range Coulomb interactions to bimolecular luminescence quenching reactions

Newsham¹,

Cukier²,

Nocera³

1991

J. Phys. Chem.

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“…Since the photophysical properties of¯uorophores that are complexed with metals are distinctly different from those of the¯uorophores themselves (Lo È hr & Vo È gtle, 1985;Thanabal & Krishnan, 1982;Tundo & Fendler, 1980;Ghosh et al, 1988), such complexes are of potential application as laser dyes, frequency converters and ion-recognition agents (Bourson & Valeur, 1989;Bourson et al, 1982Bourson et al, , 1983Ernsting et al, 1988). Among the¯uoroionophores, the most studied are courmarin derivatives (Bourson & Valeur, 1989); in their complexes, the light-emitting ability is expected to depend on the metal atom itself.…”

Section: Commentmentioning

confidence: 99%

Bis[3-(4-methylcoumarinyl-7-oxy)-μ-methoxy-1,1,3,3-tetramethyldistannoxane]

et al. 2003

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“…The implications for realizing intramolecular ETDL systems were also discussed, including studies of the picosecond dynamics of the intra-EET process. [298][299][300][301][302][303][304][305] Related studies deal with intramolecular quenching processes, 306 with intramolecular exciplex formation, 206,207,209,307 with intramolecular photochemical reactions in bichromophoric molecular systems, 57,308 in studies of biological systems, 309 and of intra-EET in bichromophoric compounds of transition metals [310][311][312][313][314][315][316][317] and chelates. 318 Of particular interest are the studies carried out by Hochstrasser and co-workers where femtosecond excitation was used to follow the rate of intra-EET in 9′,9-bifluorene and 2′,2-binaphthyl in a variety of solvents.…”

Section: B Short-range Singlet−singlet Energy Transfermentioning

confidence: 99%

“… ,, They used EET as a probe to gain experimental proof for calculated statistical distributions of conformations of the flexible polymethylene chains connecting donor and acceptor chromophores. The implications for realizing intramolecular ETDL systems were also discussed, including studies of the picosecond dynamics of the intra-EET process. − Related studies deal with intramolecular quenching processes, with intramolecular exciplex formation, ,,, with intramolecular photochemical reactions in bichromophoric molecular systems, , in studies of biological systems, and of intra-EET in bichromophoric compounds of transition metals − and chelates …”

Section: B Short-range Singlet−singlet Energy Transfermentioning

confidence: 99%

Photophysics and Mechanisms of Intramolecular Electronic Energy Transfer in Bichromophoric Molecular Systems: Solution and Supersonic Jet Studies

1996

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Sub-picosecond time-resolved intramolecular electronic energy transfer in bichromophoric rhodamine dyes in solution

Cited by 24 publications

References 23 publications

Contribution of long-range Coulomb interactions to bimolecular luminescence quenching reactions

Contribution of long-range Coulomb interactions to bimolecular luminescence quenching reactions

Bis[3-(4-methylcoumarinyl-7-oxy)-μ-methoxy-1,1,3,3-tetramethyldistannoxane]

Photophysics and Mechanisms of Intramolecular Electronic Energy Transfer in Bichromophoric Molecular Systems: Solution and Supersonic Jet Studies

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