Picosecond kinetics of the excited-state, proton-transfer reaction of 1-naphthol in water

Webb, S. P.; Philips, Laura A.; Yeh, Sung-Wei; Tolbert, Laren M.; Clark, J. H.

doi:10.1021/j100412a053

Cited by 127 publications

(129 citation statements)

References 0 publications

Supporting

Mentioning

120

Contrasting

Order By: Relevance

“…Previous studies indicated that the frequency of the C-O stretch mode appears in the 1400-1600 cm À1 range assigned to a ππ* nature triplet state and in the 1200-1400 cm À1 region as a typical nπ* nature triplet state. [29][30][31][32][33] As illustrated above, the C-O stretching frequency for 3 SPF is located at 1413 cm À1 , and this indicates the 3 SPF possesses a ππ* electronic configuration. Inspection of Fig.…”

Section: Nanosecond-tr 3 Study In Mecnmentioning

confidence: 99%

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

Zhu

Xue

et al. 2014

J Raman Spectroscopy

View full text Add to dashboard Cite

The photochemistry of suprofen (SPF) was investigated by femtosecond transient absorption (fs-TA), resonance Raman (RR) and nanosecond time-resolved resonance Raman (ns-TR 3 ) spectroscopic methods to gain additional information so as to better elucidate the possible photochemical reaction mechanism of suprofen in several different solvents. In neat acetonitrile (MeCN), the fs-TA and ns-TR 3 experimental data indicated that the lowest lying excited singlet state S 1 (nπ*) underwent an efficient intersystem crossing process (ISC) to the excited triplet state T 3 (ππ*), followed by an internal conversion (IC) process to T 1 (ππ*). In the aqueous solution, a triplet biradical species ( 3 ETK-1) was obtained as the product of a decarboxylation process from triplet suprofen anion ( 3 SPF À ) and the reaction rate of the decarboxylation process was determined by the concentration of H 2 O. A protonation process for 3 ETK-1 leads to formation of a neutral species ( 3 ETK-3) that was directly observed by ns-TR 3 spectra, then this 3 ETK-3 species decayed via ISC process to generate final product.

show abstract

Section: Nanosecond-tr 3 Study In Mecnmentioning

confidence: 99%

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

Zhu

Xue

et al. 2014

J Raman Spectroscopy

View full text Add to dashboard Cite

show abstract

“…Here the pK A value of the molecule in the ground state is 9.4 while the corresponding value in the S 1 is only 0.5. The mechanism of the proton transfer from the NP molecule to the solvent leading to an enhancement of the acidity in the excited state has been investigated in a series of publications in the liquid phase [1][2][3][4] and more recently in clusters. [5][6][7][8][9][10][11][12][13][14][15] Several spectroscopic experiments have been carried out to understand the mechanism of molecule-solvent interactions.…”

Section: Introductionmentioning

confidence: 99%

“…[18][19][20] The energy of the trans configuration in the ground state is 220 ( 50 cm -1 lower than the ground state of the cis rotamer. 18 The rate constants for the proton separation were determined in solution, 3,21 in Ar matrix, 22 and in femtosecond pump/probe experiments with clusters of NP with water, NH 3 , and piperidine. 11 In the present work, additional information on the S 1 electronic state is obtained from ionic spectra measured via different intermediate vibronic states in S 1 with the technique of mass-analyzed threshold ionization (MATI) after resonanceenhanced two-photon ionization.…”

Section: Introductionmentioning

confidence: 99%

Mass-Analyzed Threshold Ionization of the trans-1-Naphthol−Water Complex: Assignment of Vibrational Modes, Ionization Energy, and Binding Energy

Braun

Neusser

2003

J. Phys. Chem. A

View full text Add to dashboard Cite

Naphthol is a prototype example for the enhancement of the molecule-to-solvent proton transfer after electronic excitation. In this work, we investigate the influence of water molecules attached to naphthol on the spectroscopic properties of the neutral excited-state S 1 and the ionic state. In addition to S 1 rS 0 spectra, we present mass-analyzed threshold ionization (MATI) spectra for 1-naphthol and for the first time of the 1-naphthol‚H 2 O complex displaying a rich variety of intra-and intermolecular vibrational bands. The comparison of ionic spectra measured via different intermediate states allows us to assign various vibrational modes in the monomer and the 1-naphthol‚H 2 O cluster assuming a ∆ν ) 0 propensity rule. Assignment is also based on the energies and atomic displacement patterns of vibrations calculated from ab initio theory.

show abstract

“…13.3 suggested that reprotonation should occur at C-5 or C-8. Indeed, we observed that 1-naphthol undergoes efficient H/D exchange at C-5 and C-8, with significant preference for the C-5 position [12]. In contrast, 2-naphthol exhibits little or no proton quenching and a "normal" pK a * of 2.8, a fact which has been attributed to the diffuse nature of the latter and a more localized L a for the former.…”

Section: -Naphthol Vs 2-naphtholmentioning

confidence: 75%

Design and Implementation of “Super” Photoacids

Tolbert

Solntsev

2006

Hydrogen‐Transfer Reactions

Self Cite

View full text Add to dashboard Cite

Electron and proton transfer (see Eqs. (13.1) and (13.2), involve obvious similarities. When the starting materials are neutral, both result in the formation of charge and in the necessity for separation of charge to stabilize the product states. In principle, both can occur in the ground state, but transfer that is exoergic only in the excited state allows the use of time-resolved spectroscopic techniques to determine the details of solvation and structural reorganization. For electron transfer, the development of such techniques and the accompanying theoretical rationale, most especially the Marcus theory, has been one of the triumphs of modern mechanistic chemistry.The relationship between driving force and proton transfer has been much more elusive despite considerable evidence that the vast photosynthetic electron transfer machinery mainly exists to set up a charge gradient to drive proton transfer. This is due to a combination of two factors. First, there is a vast reservoir of readily available materials with which to examine electron transfer. Second, the relationship between rates and driving force for electron transfer, based upon the excitation energies and the relevant redox potentials (the Rehm-Weller equation [1]) is reasonably straightforward. In contrast, the relationship between rates and driving force for excited-state pK a * ¼ pK a À DE o;o =2: 3RT (13.3) proton transfer (based upon relative pK a s and calculated through the Förster equation, Eq. (13.3) [2]) is less straightforward. For instance, the existence of a so-called "inverted" region for proton transfer has been the subject of much controversyHydrogen-Transfer Reactions. Edited by

show abstract

Picosecond kinetics of the excited-state, proton-transfer reaction of 1-naphthol in water

Cited by 127 publications

References 0 publications

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

Time‐resolved spectroscopic and density functional theory investigation of the photochemistry of suprofen

Mass-Analyzed Threshold Ionization of the trans-1-Naphthol−Water Complex: Assignment of Vibrational Modes, Ionization Energy, and Binding Energy

Design and Implementation of “Super” Photoacids

Contact Info

Product

Resources

About