Indoline: a versatile probe of specific and non-specific solvation forces

Esentürk, Okan; Walker, Robert A.

doi:10.1039/b301358h

Cited by 4 publications

(4 citation statements)

References 35 publications

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“…The resulting larger change in permanent dipole leads to a shift in excitation to lower energies (and longer wavelength). In contrast, the hydrogen bond donating property of water stabilizes indoline in its ground state thereby increasing the energetic gap between ground and excited electronic states leading to the experimentally observed blue shift in excitation wavelength. ,, …”

Section: Resultsmentioning

confidence: 99%

“…In contrast, the hydrogen bond donating property of water stabilizes indoline in its ground state thereby increasing the energetic gap between ground and excited electronic states leading to the experimentally observed blue shift in excitation wavelength. 21,56,57…”

Section: Electronic Structure Calculationsmentioning

confidence: 99%

“…Again, many studies have proposed empirical scales to treat the effects of specific solvation interactions on solute chemistry, but only a few of these efforts have resulted in models that are sufficiently general to cover a variety of solutes solvated by many different classes of solvents. 13,[20][21][22] At solid/liquid interfaces one expects both nonspecific and specific solvation interactions to be different than in bulk solution. First, depending on the magnitudes and types of interactions, interfacial solute concentrations may be enhanced through adsorption or depleted by unfavorable energetics (such as Coulomb repulsions or hydrophobic effects).…”

Section: Introductionmentioning

confidence: 99%

“…Examples of this type of solvation include dipole−dipole, charge−dipole, and hydrogen bonding interactions. Again, many studies have proposed empirical scales to treat the effects of specific solvation interactions on solute chemistry, but only a few of these efforts have resulted in models that are sufficiently general to cover a variety of solutes solvated by many different classes of solvents. ,− …”

Section: Introductionmentioning

confidence: 99%

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Differentiating Solvation Mechanisms at Polar Solid/Liquid Interfaces

Brindza

Walker

2009

J. Am. Chem. Soc.

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Resonance enhanced second harmonic generation (SHG) has been used to identify solvation mechanisms at different solid/liquid interfaces. Solvation interactions are characterized as being either nonspecific and averaged over the entire solute cavity or specific, referring to localized, directional interactions between a solute and its surroundings. SHG spectra report the electronic structure of solutes adsorbed to silica/organic solvent interfaces, and different solutes are chosen to probe either interfacial polarity or interfacial hydrogen bond donating/accepting opportunities. SHG results show that interfacial polarity probed by p-nitroanisole depends sensitively on solvent structure, whereas hydrogen bonding interactions probed by indoline are insensitive to solvent identity and instead are dominated by the hydrogen bond donating properties of the polar silica substrate. The bulk solvation interactions were modeled with a series of ab initio calculations that characterized solute electronic structure within a dielectric continuum and in the presence of explicit, individual solvent molecules. Collectively, these measurements and calculations create a comprehensive picture of how solvation mechanisms vary at different polar, solid surfaces.

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Section: Resultsmentioning

confidence: 99%

Section: Electronic Structure Calculationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Differentiating Solvation Mechanisms at Polar Solid/Liquid Interfaces

Brindza

Walker

2009

J. Am. Chem. Soc.

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Synthesis, structures, and luminescence properties of ternary supramolecular hydrogen‐bonded complexes involving [(o‐C₆F₄)Hg]₃, carbazole, and a Lewis base

Burress

Gabbaı̈

2007

Heteroatom Chemistry

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The interaction of trimeric perfluoroortho-phenylene mercury (1) with carbazole in dichloromethane3 and 4 have been characterized by elemental analysis, IR spectroscopy, and luminescence spectroscopy. The crystal structures of 3 and 4 have also been determined. Both adducts have extended structures that exhibit supramolecular binary stacks, where molecules of 1 and the carbazole-Lewis base complex alternate. Short Hg-C contacts involving molecules of 1 and carbazole indicate the presence of secondary Hg-π interactions. In addition, adducts 3 and 4 display hydrogen-bonding interactions between the acidic N H moiety of carbazole and the heteroatom of the Lewis base. The presence of this hydrogen bond is also confirmed by IR spectroscopy, which shows that the ν N−H of 3 and 4 is lower than that of 2. The luminescence spectra of these adducts correspond to the phosphorescence of carbazole, which is induced by the mercury heavy atom effect. In the case of 3 and 4, additional low-energy bands are observed at 578 and 567

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Hydrogen-bonding molecular ruler surfactants as probes of specific solvation at liquid/liquid interfaces

2009

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Resonance-enhanced, second harmonic generation (SHG) is used to measure the electronic structure of solutes sensitive to specific solvation adsorbed to liquid/liquid and liquid/solid interfaces. Here, specific solvation refers to solvent-solute interactions that are directional and localized. N-methyl-p-methoxyaniline (NMMA) is a solute whose first allowed electronic transition wavelength remains almost constant (approximately 315 nm) in non-hydrogen-bonding solvents regardless of solvent polarity. However, in hydrogen-bond-accepting solvents such as dimethylsulfoxide, NMMA's absorbance shifts to longer wavelengths (320 nm), whereas in hydrogen-bond-donating solvents (e.g., water), the absorbance shifts to shorter wavelengths (approximately 300 nm). SHG experiments show that at alkane/silica interfaces, surface silanol groups serve as moderately strong hydrogen-bond donors as evidenced by NMMA's absorbance of 307 nm. At the carbon tetrachloride/water interface, NMMA absorbance also shifts to slightly shorter wavelengths (298 nm) implying that water molecules at this liquid/liquid interface are donating strong hydrogen bonds to the adsorbed NMMA solutes. In contrast, experiments using newly developed molecular ruler surfactants with NMMA as a model hydrophobic solute and a hydrophilic, cationic headgroup imply that, as NMMA migrates across an aqueous/alkane interface, it carries with it water that functions as a hydrogen-bond-accepting partner.

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Indoline: a versatile probe of specific and non-specific solvation forces

Cited by 4 publications

References 35 publications

Differentiating Solvation Mechanisms at Polar Solid/Liquid Interfaces

Differentiating Solvation Mechanisms at Polar Solid/Liquid Interfaces

Synthesis, structures, and luminescence properties of ternary supramolecular hydrogen‐bonded complexes involving [(o‐C₆F₄)Hg]₃, carbazole, and a Lewis base

Hydrogen-bonding molecular ruler surfactants as probes of specific solvation at liquid/liquid interfaces

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Indoline: a versatile probe of specific and non-specific solvation forces

Cited by 4 publications

References 35 publications

Differentiating Solvation Mechanisms at Polar Solid/Liquid Interfaces

Differentiating Solvation Mechanisms at Polar Solid/Liquid Interfaces

Synthesis, structures, and luminescence properties of ternary supramolecular hydrogen‐bonded complexes involving [(o‐C6F4)Hg]3, carbazole, and a Lewis base

Hydrogen-bonding molecular ruler surfactants as probes of specific solvation at liquid/liquid interfaces

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Synthesis, structures, and luminescence properties of ternary supramolecular hydrogen‐bonded complexes involving [(o‐C₆F₄)Hg]₃, carbazole, and a Lewis base