Solvatochromism, halochromism, and preferential solvation of new dipolar guaiazulenyl 1,4-benzoquinone methidesElectronic supplementary information (ESI) available: Absorption maxima of the dyes 6–10 in seven binary solvent mixtures. See http://www.rsc.org/suppdata/ob/b2/b209555f/

Laus, Gerhard; Schottenberger, Herwig; Wurst, Klaus; Schütz, Johannes; Ongania, Karl‐Hans; Horvath, Ulrike Erika Ida; Schwärzler, Alexander

doi:10.1039/b209555f

Cited by 27 publications

(11 citation statements)

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“…Here, increased solvent polarity leads to higher transition energy (negative solvatochromism). A quinoid system based on 2,6-dibromophenol displaying positive solvatochromism has been reported previously (Laus et al, 2003). …”

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confidence: 85%

(E)-2,6-Dibromo-4-{2-[1-(1H,1H,2H,2H-perfluorooctyl)pyridinium-4-yl]ethenyl}phenolate methanol disolvate, a fluoroponytailed solvatochromic dye

et al. 2017

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The title compound, C 21 H 12 Br 2 F 13 NOÁ2CH 3 OH, was obtained by condensation of 4-methyl-1-(1H,1H,2H,2H-perfluorooctyl)pyridinium iodide and 3,5-dibromo-4-hydroxybenzaldehyde, followed by deprotonation. It crystallizes as a methanol disolvate and exhibits short O-HÁ Á ÁO hydrogen bonds and a disordered perfluoroalkyl chain [occupancy ratio 0.538 (7):0.462 (7)]. Significant -stacking interactions are observed between the benzene and pyridine rings of neighbouring molecules along the b-axis direction. Chemical contextDyes with a fundamental type of conjugated system as in the title compound have long been known (Hü nig & Rosenthal, 1955). It was intended to combine the structural features of a delocalized -electron system with those of polyfluorinated compounds in order to derive a new material with advantageous properties such as altered solubility (Hoang & Mecozzi, 2004) and affinity (Wagner et al., 2016) profiles, given that the physical and chemical properties of organic compounds are strongly affected by the introduction of fluorinated substituents. Fluorosurfactants have a tendency towards micelle formation in biphasic or ternary solvent mixtures. Thus, the utilization of solvatochromic surfactants as self-indicating micelle reporters (Kedia et al., 2014) is an attractive analytical concept for fluorous-phase-related materials science. Structural commentaryThe title compound comprises a delocalized -electron system, involving either a zwitterionic benzoid or a non-polar ISSN 2056-9890 quinoid resonance structure. Inspection of bond lengths leads to the conclusion that it is not a typical cyclohexadienone system (Chandran et al., 2008;Chiverton et al., 1991) but rather a benzoid system similar to 2,6-dibromophenol predominant (Eriksson & Eriksson, 2001;Lu et al., 2011;Lehmler & Parkin, 2005). The heterocyclic ring also resembles a typical pyridinium system. Furthermore, the shortest C C bond in the bridge linking the two rings is between C6 and C7 with a length of 1.337 (6) Å , whereas the adjacent bonds are considerably longer. The framework thus is not quinoid but benzoid. The conjugated moieties of the dye molecule are almost planar and the mean planes of the benzene and pyridine rings form an angle of 2.97 (2) , whilst the fluorinated chains protrude from the plane.The carbon atoms C17-C21 and fluorine atoms F3-F13 of the polyfluorinated tail are disordered over sets of sites with an occupancy ratio for the two disorder fragments of 0.538 (7):0.462 (7). The chain adopts a slightly helical conformation (Fournier et al., 2010) with an average C-C-C-C twist angle (deviation from 180 ) of 3 . Typically, -electron donor-acceptor-substituted conjugated systems exhibit solvatochromism. Solutions of the title compound display absorption maxima at 610 nm (blue) in THF and 502 nm (red) in MeOH. Here, increased solvent polarity leads to higher transition energy (negative solvatochromism). A quinoid system based on 2,6-dibromophenol displaying positive solvatochromism has been reported previously (Laus et al....

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confidence: 85%

(E)-2,6-Dibromo-4-{2-[1-(1H,1H,2H,2H-perfluorooctyl)pyridinium-4-yl]ethenyl}phenolate methanol disolvate, a fluoroponytailed solvatochromic dye

et al. 2017

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“…A relatively small number of these cations are replaced by the charged oxygen atoms of the phenolate donor. In this purely geometric arrangement, for an average cation-oxygen distance d, the number of cations present in a cubic volume V of side a was given by N = a 3 /d 3 …”

Section: Theoretical Modelmentioning

confidence: 99%

“…It may designate the spectral behaviour of compounds in solution whose absorptions are pH-dependent [1], or of compounds which exhibit substantial changes in their UV-Vis spectra by the addition of salts [1][2][3][4].…”

Section: Introductionmentioning

confidence: 99%

The cationic halochromism of phenolate betaines: Molecular dynamics and quantum mechanics studies

Domínguez

Rezende

2010

JICS

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The cationic halochromism of phenolate betaines was reproduced with the aid of a simple theoretical model, by calculation of the longest wavelength transition energies of supermolecules obtained by positioning a cation M n+ at a variable distance from the oxygen atom of the dye. The theoretical results were compared with experimental data for three systems, Reichardt's betaine 1, Brooker's merocyanine 2 and the N-methyl-8-oxyquinolinium dye 3. The model was validated by molecular dynamics simulations of solutions of dye 3, in methanol and DMSO, in the presence of variable concentrations of Na + .

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“…5 Interestingly, the photophysical properties of a fluorescent molecule greatly were affected by a hydrogen bond, which is formed under specific conditions in between the fluorescent molecule and a protic solvent, and can greatly influence its molecular orbital energy levels. Consequently, the divergent stabilization in the ground and excited states is analogous with the shape and intensity of absorption or emission spectra, with dissimilarity in highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) positions and the changes in energy gap between the electronic states.…”

Section: Introductionmentioning

confidence: 99%

“…In solvent polarity change, the solvatochromism mainly depends upon the divergent stabilization of the chromophore both in the ground and excited states. Consequently, the divergent stabilization in the ground and excited states is analogous with the shape and intensity of absorption or emission spectra, with dissimilarity in highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) positions and the changes in energy gap between the electronic states . Interestingly, the photophysical properties of a fluorescent molecule greatly were affected by a hydrogen bond, which is formed under specific conditions in between the fluorescent molecule and a protic solvent, and can greatly influence its molecular orbital energy levels.…”

Section: Introductionmentioning

confidence: 99%

Efficient Synthesis and Characterization of Solvatochromic Fluorophore

Adnan

Kim

Jeong

et al. 2017

Bulletin Korean Chem Soc

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A highly efficient designing and synthesis of an aryl-substituted carbazole-based fluorescent material (MeOCbzBP) has been carried out via tandem carbon-carbon (C-C)/carbon-nitrogen (C-N) bond formation by multiple Suzuki couplings and Cadogan cyclization followed by C-N cross-couplings. Various organic solvents have been used to investigate photophysical, solvatofluorochromism, and photoluminescence characteristics of MeOCbzBP. The MeOCbzBP showed a reasonable redshifted absorption in UV region and photoluminescence enhancements in tetrahydrofuran/water mixtures. Furthermore, we also employed various theoretical functions to optimize the molecule both in the ground and excited states. A well-known density functional theory was employed in a solvent phase with B3LYP/6-31G(d) level of theories. We believe that the MeOCbzBP will provide a better platform to investigate the novel applications in the field of medicinal chemistry and chemical biology.

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Solvatochromism, halochromism, and preferential solvation of new dipolar guaiazulenyl 1,4-benzoquinone methidesElectronic supplementary information (ESI) available: Absorption maxima of the dyes 6–10 in seven binary solvent mixtures. See http://www.rsc.org/suppdata/ob/b2/b209555f/

Cited by 27 publications

References 38 publications

(E)-2,6-Dibromo-4-{2-[1-(1H,1H,2H,2H-perfluorooctyl)pyridinium-4-yl]ethenyl}phenolate methanol disolvate, a fluoroponytailed solvatochromic dye

(E)-2,6-Dibromo-4-{2-[1-(1H,1H,2H,2H-perfluorooctyl)pyridinium-4-yl]ethenyl}phenolate methanol disolvate, a fluoroponytailed solvatochromic dye

The cationic halochromism of phenolate betaines: Molecular dynamics and quantum mechanics studies

Efficient Synthesis and Characterization of Solvatochromic Fluorophore

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