Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Renge, Indrek

doi:10.1016/j.jlumin.2008.11.023

Cited by 5 publications

(12 citation statements)

References 27 publications

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“…To rationalize the behavior of B30 and its sensitivity against even small changes in its molecular-microscopic environment, this class of zwitterionic dyes has been repeatedly and intensively studied. ,, Nevertheless, the perichromism of these betaine dyes is far from being well understood. New findings with respect to their solvatochromic, − thermochromic, − photophysical, ,, and structural behavior have been recently reported; some of them will be commented on in this work.…”

Section: Introductionmentioning

confidence: 90%

“…Former UV/vis spectroscopic studies of B30 were mainly centered on the determination of its long-wavelength π → π* absorption in a great variety of solvents to get E T (30) values for as many solvents and solvent mixtures as possible. Some recent papers gave now further valuable information about the photophysical behavior of B30 in solution. ,, …”

Section: Introductionmentioning

confidence: 99%

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On the Molecular Structure and UV/vis Spectroscopic Properties of the Solvatochromic and Thermochromic Pyridinium-N-Phenolate Betaine Dye B30

2010

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Quantum chemical calculations as well as vis absorption and fluorescence measurements of the pyridinium-N-phenolate betaine dye B30, dissolved in 1-chlorobutane at temperatures between 343 and 77 K, shed more light on the solvatochromism, thermosolvatochromism, and photophysical behavior of this probe dye, formerly used to establish an empirical scale of solvent polarity, called E(T)(30) or E(T)(N) scale. A new calculated gas-phase E(T)(30) value is reported. Complementary to recent work of Kharlanov and Rettig (J. Phys. Chem. A 2009, 113, 10693-10703), it is shown that fluorescence of B30 in 1-chlorobutane solution is observable already at temperatures just below the solvent's melting point and not only at 77 K. Analogous to increasing solvent polarity, decreasing solvent temperature leads to a large hypsochromic shift of the vis absorption band of B30, dissolved in 1-chlorobutane (Deltalambda = -245 nm from 797 nm at 343 K to 552 nm at 77 K). This thermosolvatochromism can be easily seen: the solution color changes from greenish yellow (343 K) to magenta-violet (77 K).

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Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

On the Molecular Structure and UV/vis Spectroscopic Properties of the Solvatochromic and Thermochromic Pyridinium-N-Phenolate Betaine Dye B30

2010

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“…Betaine-30 is a highly solvatochromatic molecule which undergoes photoinduced charge transfer. 4 Its ground state geometry, which is sensitive to the solvent environment, 5,6 is stabilized as a charge separated state. The molecule undergoes ultrafast intermolecular charge transfer upon photoexcitation.…”

Section: Introductionmentioning

confidence: 99%

Excited state structural evolution during charge-transfer reactions in betaine-30

Silva

Frontiera

2016

Phys. Chem. Chem. Phys.

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Ultrafast photo-induced charge-transfer reactions are fundamental to a number of photovoltaic and photocatalytic devices, yet the multidimensional nature of the reaction coordinate makes these processes difficult to model theoretically. Here we use femtosecond stimulated Raman spectroscopy to probe experimentally the structural changes occurring following photoexcitation in betaine-30, a canonical intramolecular charge-transfer complex. We observe changes in vibrational mode frequencies and amplitudes on the femtosecond timescale, which for some modes results in frequency shifts of over 20 cm(-1) during the first 200 fs following photoexcitation. These rapid mode-specific frequency changes track the planarization of the molecule on the 400 ± 100 fs timescale. Oscillatory amplitude modulations of the observed high frequency Raman modes indicate coupling between specific high frequency and low frequency vibrational motions, which we quantify for 6 low frequency modes and 4 high frequency modes. Analysis of the mode-specific kinetics is suggestive of the existence of a newly discovered electronic state involved in a relaxation pathway, which may be a low-lying triplet state. These results directly track the multiple nuclear coordinates involved in betaine-30's reactive pathway, and should be of use in rationally designing molecular systems with rapid electron transfer processes.

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“…The two-state approximation proves to be adequate for the studied system, and allowed the observed solvent-polarity-induced decrease of the 2PA cross-section to be related to the decrease of the transition moment and the increase in the excitation energy. Noteworthy examples are the detection of a narrowing of the CT absorption band in the temperature range of 10-293 K, [66] low-temperature fluorescence, [40,72,73] or room-temperature fluorescence in the subpicosecond regime. [17,52,53] More recently, RD has gained interest as a material used for model studies of controlled drug delivery [54,55] and as a promising agent for comparing the electrophilicity of various neutral Lewis acidic species.…”

Section: Introductionmentioning

confidence: 99%

“…[1, 15-17, 38, 50, 70, 71] To date, a large variety of spectroscopic issues concerning RD and its surroundings have been addressed. Noteworthy examples are the detection of a narrowing of the CT absorption band in the temperature range of 10-293 K, [66] low-temperature fluorescence, [40,72,73] or room-temperature fluorescence in the subpicosecond regime. [78] As mentioned above and discussed in our previous works, [21,35,101] solvatochromism may also be considered in the context of 2PA for molecules in solution.…”

Section: Introductionmentioning

confidence: 99%

Two‐Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two‐Photon Absorption Spectrum of Reichardt’s Dye

et al. 2013

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In this study, we report on the influence of solvent on the two-photon absorption (2PA) spectra of Reichardt's dye (RD). The measurement of 2PA cross-sections is performed for three solvents (chloroform, dimethyl formamide, and dimethyl sulfoxide) using the Z-scan technique. The key finding of this study is the observation that the cross-section, corresponding to the 2PA of the intramolecular charge-transfer state, diminishes substantially upon increasing the solvent polarity. To unravel the solvent dependence of the 2PA cross-section, the electronic structure of RD is determined using a hybrid quantum mechanics/molecular mechanics (QM/MM) approach, in which polarization between the solute and solvent is taken into account by using a self-consistent scheme in the solvent polarization. The two-state approximation proves to be adequate for the studied system, and allowed the observed solvent-polarity-induced decrease of the 2PA cross-section to be related to the decrease of the transition moment and the increase in the excitation energy.

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Motional narrowing of broadband absorption of solvatochromic indicator Betaine 30

Cited by 5 publications

References 27 publications

On the Molecular Structure and UV/vis Spectroscopic Properties of the Solvatochromic and Thermochromic Pyridinium-N-Phenolate Betaine Dye B30

On the Molecular Structure and UV/vis Spectroscopic Properties of the Solvatochromic and Thermochromic Pyridinium-N-Phenolate Betaine Dye B30

Excited state structural evolution during charge-transfer reactions in betaine-30

Two‐Photon Solvatochromism II: Experimental and Theoretical Study of Solvent Effects on the Two‐Photon Absorption Spectrum of Reichardt’s Dye

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