Hydrogen Bond Formation between 4-(Dimethylamino)pyridine and Aliphatic Alcohols

Demeter, Attila; Mile, Viktória; Bérces, T.

doi:10.1021/jp072989i

Cited by 17 publications

(28 citation statements)

References 33 publications

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“…The partial charge on the pyridine nitrogen decreases in the 'b' complexes and increases in the 'a' and especially in the 'c' cases. This observation is in accordance with our previous findings 15 that the formation of the 'c' type hydrogen bond enhances the charge separation in the ground state, and increases the negative partial charge on the pyridine nitrogen.…”

Section: (Table 5)supporting

confidence: 94%

“…We present dipole moments and vibration frequencies as well, because these data are rather useful in the data evaluation of experimental spectra. 15 Those data are selected, which are supposed to change significantly during the complex formation.…”

Section: (Table 1)mentioning

confidence: 99%

“…It was concluded that the excited molecule emits dual luminescence with the characteristics of the reversible two-state systems in polar solvents, while the long wavelength fluorescence is almost unobservable in nhexane. 8,9,[13][14][15] An experimental study has been published recently on the photolysis of DMAP in the presence and absence of different aliphatic alcohols and fluorinated aliphatic alcohols in various solvents by the authors of this paper. 15 As an effect of hydrogen bond formation in the apolar n-hexane the ICT emission becomes dominant, while in polar solvents a polarity dependent red shift is observable, indicating a strong increase of the excited state dipole moment of the ICT state with complexation.…”

Section: Introductionmentioning

confidence: 99%

“…8,9,[13][14][15] An experimental study has been published recently on the photolysis of DMAP in the presence and absence of different aliphatic alcohols and fluorinated aliphatic alcohols in various solvents by the authors of this paper. 15 As an effect of hydrogen bond formation in the apolar n-hexane the ICT emission becomes dominant, while in polar solvents a polarity dependent red shift is observable, indicating a strong increase of the excited state dipole moment of the ICT state with complexation. It was indicated, that the magnitude of the experimentally derived dipole moment of the ICT state of DMAP and its singly complex derivative (in apolar solvents) favours more the occurrence of the planar structure of the species in question.…”

Section: Introductionmentioning

confidence: 99%

“…The calculations were accomplished mostly for gas-phase complexes, but for a few systems simple solvent models were included to get some indication on the effect of solvation. Ground-state dipole moments of the complexed molecules were estimated, in order to provide data for the evaluation of previous 15 and further experimental data. A possible step of further investigations might be a set of systematic and comprehensive excited state calculations on the complexes.…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemical study of the ground-state alcoholic complexation of selected dual luminescent compounds

Mile¹,

Demeter²,

Tóth³

2009

Molecular Physics

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The ground and excited state features of dual luminescent molecules are strongly influenced by the presence of alcoholic additives. Selected ground state properties of methanol and 1,1,1,3,3,3-hexafluoro-propan-2-ol complexes of 4-aminobenzonitrile, 4-aminopyridine and aniline derivatives are obtained by quantum chemical calculations. The formation enthalpies of the complexes are the most exothermic when the cyano or ring nitrogen interacts by the hydroxyl group of the alcohols. The binding energies are almost doubled when the fluorinated reactant is the hydrogen bond donor. Parallel with the enhancement of the stabilization of the complex, the ground state dipole moment also increases notably with the complex formation. In principle, consideration of this enlargement is essential in interpretation of the solvatochromatic behaviour of the complexed species.

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Section: (Table 5)supporting

confidence: 94%

Section: (Table 1)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Quantum chemical study of the ground-state alcoholic complexation of selected dual luminescent compounds

Mile¹,

Demeter²,

Tóth³

2009

Molecular Physics

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Hydrogen Bond Basicity in the Excited State: Concept and Applications

Demeter

2010

Hydrogen Bonding and Transfer in the Excited State

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Hydrogen-bonded complex formation often modifies significantly the physicochemical, spectroscopic and kinetic properties of organics. This observation is even more straightforwardly valid if the properties of the electronic excited states are considered. When the solvents have protic character, the absorption and emission maxima of the fluorophores shift out from the usual range; in addition, the quantum yields and the lifetimes of the excited molecules are often very dissimilar to those expected in solvents of comparable polarity. The first step to account for these phenomena is to construct a proper thermodynamic description of the excited-state hydrogen bonding process; however, relatively little effort has been made to develop a concise handling. The difficulties probably originate from the complex nature of the interaction (weak, competing solute-solvent and solvent-solvent interactions, where the distribution of the interaction energies are comparable), and from the fact that the lifetimes of the excited states are in the same range than the characteristic time of the processes in question.In this chapter, an inchoative but consistent methodology for dealing with this phenomenon is shown. Model systems where the effects are great enough for clear conclusions to be drawn and where disturbing side processes are probably negligible were chosen for examination. The hydrogen bond forming reactants were aliphatic alcohols, mostly fluorinated ones. By using a homologue series of alcohols, the effect of reaction enthalpy can be kept under control. The solvents used in this study were exclusively aprotic, first and foremost n-hexane. In paraffin solvents, not only are the solvent-solute and solvent-reactant interactions negligible but also the examined effects and interactions are much more pronounced.

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On the influence of unsaturation on the macrolactonization of hydroxy fatty acids

Caruso¹,

Donnamaria²,

Artillo³

et al. 2009

J of Physical Organic Chem

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Regioselectivity and yields of Yamaguchi cyclization of (15S,16S)-15,16-dihydroxy-otadecyl-(6Z,9Z,12Z)-trienoic acid and its saturated homologue have been compared at different temperatures and concentrations. For the unsaturated species the regioselectivity of cyclization depends on temperature to such an extent that the preferred regioisomer changes as the temperature changes, whereas for the saturated homologue the even-membered ring turns out to be always the preferred one. Molecular mechanics is used to interpret these findings. For both dihydroxyacids, there is experimental evidence that the yields of the two monocyclic regioisomers are thermodynamically controlled, unlike those of the analogue monohydroxy lactones. The higher cyclization yield of the unsaturated monohydroxyacid is interpreted in terms of conformational pre-organization.

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Hydrogen Bond Formation between 4-(Dimethylamino)pyridine and Aliphatic Alcohols

Cited by 17 publications

References 33 publications

Quantum chemical study of the ground-state alcoholic complexation of selected dual luminescent compounds

Quantum chemical study of the ground-state alcoholic complexation of selected dual luminescent compounds

Hydrogen Bond Basicity in the Excited State: Concept and Applications

On the influence of unsaturation on the macrolactonization of hydroxy fatty acids

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