Empirical Treatment of the Inductive and Dispersive Components of Solute−Solvent Interactions: The Solvent Polarizability (SP) Scale

Catalán, Javier; Hopf, Henning

doi:10.1002/ejoc.200400311

Cited by 154 publications

(113 citation statements)

References 37 publications

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“…Also, because the 0-0 component of ttbP9 can be measured precisely in any type of medium, the compound can in principle be used as an accurate molecular thermometer. [25] As can be seen from Figure 1, the electronic transition 1 1 A g !1 1 B u in ttbP9 is highly structured and spans a broad spectral range (360-490 nm).…”

Section: Methodsmentioning

confidence: 92%

Electronic Energy Levels in all‐trans Long Linear Polyenes: The Case of the 3,20‐Di(tert‐butyl)‐2,2,21,21‐tetramethyl‐all‐trans‐3,5,7,9,11,13,15,17,19‐docosanonaen (ttbp9) Conforming to Kasha's Rule

Catalán

Hopf

Mlynek

et al. 2005

Chemistry A European J

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The absorption, fluorescence and fluorescence excitation spectra for 3,20-di(tert-butyl)-2,2,21,21-tetramethyl-all-trans-3,5,7,9,11,13,15,17,19-docosanonaen (ttbP9) in dilute solutions of 2-methylbutane were recorded at temperatures over the range 120-280 K. The high photostability of this nonaene allows us to assert that it exhibits a single fluorescence and that this can be unequivocally assigned to emission from its 1(1)B(u) excited state, it being the first excited electronic state. Available photophysical data for this polyene and the wealth of information reported for shorter all-trans polyenes allow us to conclude that if the first excited electronic state for the chromophore possessed 2(1)A(g) symmetry, then the energy of such a state might have been so close to that of the 1(1)B(u) state that: 1) the radiationless internal conversion mechanism would preclude the observation of the emission from the 1(1)B(u) state reported in this work and 2) the 2(1)A(g) state reached through internal conversion would be vibrationally coupled to 1(1)B(u) and would facilitate the detection of the emission from 2(1)A(g), which was not observed in any of the solvents used in this work. The spectroscopic and photochemical implications of these findings for other polyenes are discussed.

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Section: Methodsmentioning

confidence: 92%

Electronic Energy Levels in all‐trans Long Linear Polyenes: The Case of the 3,20‐Di(tert‐butyl)‐2,2,21,21‐tetramethyl‐all‐trans‐3,5,7,9,11,13,15,17,19‐docosanonaen (ttbp9) Conforming to Kasha's Rule

Catalán

Hopf

Mlynek

et al. 2005

Chemistry A European J

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“…33 SdP, 33 SP, 34 SA, 35,36 and SB 37 characterize the dipolarity, polarizability, acidity, and basicity, respectively, of a certain solvent (eq 5c). Table 2.…”

Section: Resultsmentioning

confidence: 99%

3,5-Dianilino Substituted Difluoroboron Dipyrromethene: Synthesis, Spectroscopy, Photophysics, Crystal Structure, Electrochemistry, and Quantum-Chemical Calculations

et al. 2009

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4,4-Difluoro-3,5-bis(phenylamino)-8-(4-tolyl)-4-bora-3a,4a-diaza-s-indacene (1), a symmetric fluorescent difluoroboron dipyrromethene dye, has been synthesized by nucleophilic substitution of 3,5-dichloro-4,4-difluoro-8-(4-tolyl)-4-bora-3a,4a-diaza-s-indacene with aniline. The solvent-dependent spectroscopic and photophysical properties have been investigated by means of UV-vis spectrophotometry and steady-state and time-resolved fluorometry and are compared to those of the nonsymmetrically substituted 5-chloro-4,4-difluoro-3-phenylamino-8-(4-tolyl)-4-bora-3a,4a-diaza-s-indacene (2). A new, generalized treatment of the solvent effect, proposed by Catalán (J. Phys. Chem. B 2009, 113, 5951-5960) and based on a set of four mutually independent, empirical scales (dipolarity, polarizability, acidity, and basicity of the medium) is the most appropriate for describing the solvatochromic shifts of the UV-vis absorption and fluorescence emission of 1 and 2. In contrast to the nonsymmetric compound 2, the symmetric dye 1 has higher fluorescence quantum yields (0.45-0.86) and longer fluorescence lifetimes (3.36-4.03 ns) in all solvents studied and its emission maxima are shifted bathochromically by ∼45 nm. Large differences are also evident in the redox electrochemistry of the two dyes, with the symmetric analogue 1 possessing a much lower oxidation potential (∼600 mV) than the nonsymmetric 2. The absorption bandwidths and Stokes shifts of symmetric 1 are much smaller than those for nonsymmetric 2. For both dyes, the value of the fluorescence rate constant, [k f ) (1.7 ( 0.3) × 10 8 s], does not depend much on the solvent tested. X-ray diffraction analysis of 1 shows that the BODIPY core possesses a planar structure. Quantum-chemical calculations support the different photophysical behavior of the symmetric derivative 1 vis-à-vis the nonsymmetric 2.

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“…In this work, we studied the solvatochromism of indazole in 22 different solvents of variable dipolarity (SdP), polarizability (SP), acidity (SA) and basicity (SB) as measured on the empirical scales previously developed by our research group [17][18][19][20] and compared the results with those for 1-methylindazole. Measurements were additionally made in 1-chlorobutane (ClB) at temperatures from 273 to 153 K and in 2-methylbutane (2MB) at 298-248 K in order to assess the sensitivity of indazole to the polarizability and dipolarity of the medium.…”

Section: Methodsmentioning

confidence: 99%

On the solvatochromism, dimerization and tautomerism of indazole

Catalán¹

2013

Arkivoc

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A careful study of the solvatochromism of indazole was for the first time conducted in this work. The study revealed that indazole solvatochromism is governed mainly by the polarizability of the medium and, to a lesser extent, by its acidity and basicity. Based on the results of the solvatochromic analysis and their processing with Abe's model, this polar compound undergoes no significant change in dipole moment from its ground electronic state to its first excited state, which contradicts the predictions of other authors. Indazole dimerizes in both 2-methylbutane and 1-chlorobutane. However, neither its monomer nor its dimer undergoes tautomerization to 2H-indazole in the ground state in response to an increase in dipolarity of the medium. Also, based on experimental evidence, no tautomerization occurs in the first excited singlet or triplet of the compound.

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Empirical Treatment of the Inductive and Dispersive Components of Solute−Solvent Interactions: The Solvent Polarizability (SP) Scale

Cited by 154 publications

References 37 publications

Electronic Energy Levels in all‐trans Long Linear Polyenes: The Case of the 3,20‐Di(tert‐butyl)‐2,2,21,21‐tetramethyl‐all‐trans‐3,5,7,9,11,13,15,17,19‐docosanonaen (ttbp9) Conforming to Kasha's Rule

Electronic Energy Levels in all‐trans Long Linear Polyenes: The Case of the 3,20‐Di(tert‐butyl)‐2,2,21,21‐tetramethyl‐all‐trans‐3,5,7,9,11,13,15,17,19‐docosanonaen (ttbp9) Conforming to Kasha's Rule

3,5-Dianilino Substituted Difluoroboron Dipyrromethene: Synthesis, Spectroscopy, Photophysics, Crystal Structure, Electrochemistry, and Quantum-Chemical Calculations

On the solvatochromism, dimerization and tautomerism of indazole

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