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Early events associated with the excited state proton transfer in 2-(-pyridyl)benzimidazole
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10.1063/1.3177457
/content/aip/journal/jcp/131/3/10.1063/1.3177457
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/3/10.1063/1.3177457

Figures

Image of Scheme 1.
Scheme 1.

The species involved in the ESPT of 2PBI.

Image of FIG. 1.
FIG. 1.

(a) Absorption spectra of 2PBI in aqueous solution of with (i) no sucrose (solid line) and (ii) 35% sucrose solution (dotted line). (b) Fluorescence spectra of 2PBI in glycerol-water mixtures of various compositions [% glycerol (v/v)]. (c) Fluorescence spectra in aqueous solution with with (i) no sucrose and (ii) 35% sucrose. All fluorescence spectra are corrected for fluctuations in the absorbance at .

Image of FIG. 2.
FIG. 2.

(a) Variation in the ratio of relative fluorescence quantum yields of tautomer and cationic species in glycerol-water mixtures (○), in sucrose-water solution at different percentage of sucrose (●), and in methanol-water solution as a function of logarithm of viscosity. (b) Variation in the ratio of relative fluorescence quantum yields of tautomer and cationic species in glycerol-water mixtures (○), in sucrose-water solution at different percentage of sucrose (●), and in methanol-water solution as a function of dielectric constant .

Image of FIG. 3.
FIG. 3.

Energetics for the rotation of cationic form of 2PBI; in the ground state (a) using and (b) in first excited singlet state using level of theories and (c) that of tautomer form of 2PBI in first excited singlet state using level of theories. The geometry has been optimized at each value of dihedral angle. The energy at zero dihedral angle is set to zero.

Image of FIG. 4.
FIG. 4.

(a) The fluorescence decays of 2PBI in aqueous solution containing (i) 0% and (ii) 50% glycerol: and . (b) The fluorescence decays of 2PBI in deuterated oxide at at 380 and 460 nm: in all cases.

Image of FIG. 5.
FIG. 5.

The fluorescence decays of 2PBI in aqueous solution containing (i) 0% and (ii) 35% sucrose solution at (a) and (b) 460 nm. (c) The fluorescence decays of 2PBI in aqueous solutions at at 380 and 460 nm: in all cases.

Image of FIG. 6.
FIG. 6.

Variation in the logarithm of the nonradiative rate of 2PBI with the viscosity of aqueous sucrose solutions at : (upper panel) and 460 nm (lower panel).

Image of FIG. 7.
FIG. 7.

TRANES of 2PBI in 35% sucrose solution of between time 0 and 3.0 ns at intervals of 0.5 ns. The arrows indicate the direction of an increase in time.

Image of FIG. 8.
FIG. 8.

Femtosecond fluorescence transients of 2PBI at in aqueous solution of (a) , (b) , and (c) containing and (d) containing : . The solid lines denote the lines of best fit. The fitting parameters are provided in Table II. The cross-correlation function of the laser pulse is shifted for the sake of clarity.

Image of FIG. 9.
FIG. 9.

Femtosecond fluorescence transients at in the absence and presence of 35% of sucrose. (a) (b) 460 nm. . The solid lines denote the lines of best fit.

Image of FIG. 10.
FIG. 10.

Fluorescence anisotropy decay at in the absence (a) and presence (b) of 35% of sucrose. and 460 nm. . The solid lines denote the best fit to the experimental data.

Tables

Generic image for table
Table I.

Ratio of the relative quantum yield of monocation and tautomer in water-methanol mixture, water-glycerol mixture, and water-sucrose mixture in . The dielectric constants and the viscosities of the mixtures are also provided.

Generic image for table
Table II.

Temporal characteristics of 2PBI in containing different percentages of sucrose (w/w) glycerol (v/v) in solution. The data in the solution with are also shown in this table. These data are obtained from the TCSPC experiment.

Generic image for table
Table III.

Temporal characteristics of 2PBI in and at . The acid used is in the aqueous solution and in the solution.

Generic image for table
Table IV.

Early time decay parameters of 2PBI obtained from the fluorescence upconversion experiment. The lifetimes have been classified in the columns according to their values.

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/content/aip/journal/jcp/131/3/10.1063/1.3177457
2009-07-16
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Early events associated with the excited state proton transfer in 2-(2′-pyridyl)benzimidazole
http://aip.metastore.ingenta.com/content/aip/journal/jcp/131/3/10.1063/1.3177457
10.1063/1.3177457
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