Hydrogen bonding by protic solvents to nitro oxygens.  Effects on electronic spectra of nitroaniline derivatives

Kamlet, Mortimer J.; Kayser, Eleonore G.; Eastes, John W.; Gilligan, William H.

doi:10.1021/ja00797a019

Cited by 38 publications

(14 citation statements)

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“…The widely studied p-(N,N-dialkylamino)nitrobenzene chromophore [16] was chosen to probe the polarity around the hydrocarbon dendrons. Our plan was to replace one of the alkyl groups with the shorter aliphatic hydrocarbon dendrons G1-G3 (n = 1) to produce the dendritic S-Gn-probe.…”

Section: Synthesis Of Dendritic Solvatochromic Probesmentioning

confidence: 99%

The Effects of Microenvironment Polarity and Dendritic Branching of Aliphatic Hydrocarbon Dendrons on the Self‐Assembly of 2‐Ureido‐4‐pyrimidinones

Wong

Choi

Yim

et al. 2010

Chemistry An Asian Journal

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complicating interferences, the variation of the binding strength across the different generation of UPys should arise solely from dendritic microenvironment and steric effects. These two series of compounds differ from one another in the proximity of the dendron to the central UPy unit. The first set of compounds S-Gn contains a methylene spacer between the UPy and the first branching point of the dendron, while the second L-Gn has a longer trimethylene spacer. Hence, the steric effect of the dendron should be less felt by the UPy unit in the latter series. We also examined the microenvironment of these hydrocarbon dendrons by carrying out solvatochromic studies on dendritic p-nitro-A C H T U N G T R E N N U N G aniline derivatives (S-Gn-probe) of the shorter chain S-Gn series. Based on these studies, we report that a) the polarity of the microenvironment of the three generation of hydrocarbon dendrons are nearly the same, b) all dendrons can preserve the dimerization strength (K dim* = 10 7 m À1 ) of the DDAA UPy tautomers at 25 8C, and for the dendrons L-Gn with a longer spacer, even at 50 8C, c) the % amount of DADA tautomer is different for these two series of compounds, and is also temperature dependent, d) the lower limits on K' dim* of the weaker DADA tautomers are found to be 10 5 -10 6 m À1 , and e) the proximity of the dendritic branching show that the UPy unit also exerts some effect on the binding strength. Hence the K dim* values of the (L-Gn) 2 are two times higher than those of the (S-Gn) 2 series in 10 % [D 6 ]DMSO/CDCl 3 solution. Our experimental findings show that the microenvironment polarity and the dendritic branching can have significant influence on the binding strength and profile in supramolecular hydrogen bonding.

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Section: Synthesis Of Dendritic Solvatochromic Probesmentioning

confidence: 99%

The Effects of Microenvironment Polarity and Dendritic Branching of Aliphatic Hydrocarbon Dendrons on the Self‐Assembly of 2‐Ureido‐4‐pyrimidinones

Wong

Choi

Yim

et al. 2010

Chemistry An Asian Journal

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“…Moreover, due to the localization of the p-bonds in heptalenes, p-substituents, in 1,2 or 1,4 relation at one of the seven-membered rings, may interact in-phase or out-of-phase with the excited state, which should lead to strong or weak oscillator strengths of the considered electronic transition as has been demonstrated already in our earlier publications [1] as well as here, specifically in the case of 8i and 8'i. [19]; own measurements in italics. c ) Values taken from [20].…”

Section: Structural and Spectroscopicmentioning

confidence: 99%

A Spectroscopic Investigation of Donor-Acceptor-Substituted Heptalenes

Ott

Hansen

2001

HCA

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“…51 cal.mol -1 . Comparatively, the excitation energy of the spectrum of the same dye is shifted from ν max = 32.94 kK to ν max = 32.89 kK on going from tert-butyl alcohol to ethanol as solvent23, corresponding to a solvent-induced change of 143 cal.mol -1 . Moreover, the sensitivity of the technique can be increased by the addition of salts, solute concentration, or choice of dye.…”

mentioning

confidence: 94%

“…The dyes chosen for the present work were 4-nitroanisole, N,N -diethyl-4-nitroaniline, and 4-nitroaniline. Not only the electronic transitions of these dyes are responsive to different interactions in aqueous environment22–23, but also they have adequate water solubility, present intense bands transitions in experimentally accessible regions of the spectrum, and have positions of λ max minimally influenced by band overlap 22…”

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confidence: 99%

Solvatochromism as a new tool to distinguish structurally similar compounds

Madeira

Loureiro

Freire

et al. 2019

Journal of Molecular Liquids

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It is here reported a new concept based on solvatochromism to distinguish structurally similar compounds in aqueous solutions by the analysis of the stabilization of electronic excited states. The sensitivity of this approach to differentiate similar organic compounds, such as structural isomers or compound differing in the number of methylene groups, or proteins with conformational changes induced by being or not bound to cofactors, differing in two amino acids substitutions, or differing in their glycosylation profile, is demonstrated. The sensitivity of the proposed approach, based on the solvatochromic method, opens the path to its use as an auxiliary analytical tool in biomedical diagnosis/prognosis or in quality control of biologic-based drugs.

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Hydrogen bonding by protic solvents to nitro oxygens. Effects on electronic spectra of nitroaniline derivatives

Cited by 38 publications

References 1 publication

The Effects of Microenvironment Polarity and Dendritic Branching of Aliphatic Hydrocarbon Dendrons on the Self‐Assembly of 2‐Ureido‐4‐pyrimidinones

The Effects of Microenvironment Polarity and Dendritic Branching of Aliphatic Hydrocarbon Dendrons on the Self‐Assembly of 2‐Ureido‐4‐pyrimidinones

A Spectroscopic Investigation of Donor-Acceptor-Substituted Heptalenes

Solvatochromism as a new tool to distinguish structurally similar compounds

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