Hydrogen-bonding interactions of photoacids: correlation of optical solvatochromism with IR absorption spectra

Magnes, Ben‐Zion; Pines, Dina; Strashnikova, Natalia V.; Pines, Ehud

doi:10.1016/j.ssi.2003.02.001

Cited by 19 publications

(18 citation statements)

References 40 publications

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“…12.6. The situation is more complex when two different singlet states are involved in the photon-absorption and photon-emission processes of the photoacid [76,[89][90][91][92][93][94][95][96]. In cases where the vertically accessed excited state level of the photoacid and the relaxed excited state level of the photoacid are both the relatively nonpolar 1 L b state the difference between the calculated value and the thermodynamic value of pK * a is expected to be small.…”

Section: (A )*+ H +mentioning

confidence: 99%

Solvent Assisted Photoacidity

Pines

2006

Hydrogen‐Transfer Reactions

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Section: (A )*+ H +mentioning

confidence: 99%

Solvent Assisted Photoacidity

Pines

2006

Hydrogen‐Transfer Reactions

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“…This was estimated by correlating the IR and fluorescence spectra of the probe molecule in various solvents according to the K-T procedure, [39] allowing estimates for each solvent-solute system of the relative importance of the hydrogen-bonding interactions out of the total solvent-solute interactions.…”

Section: Identifying Hydrogen-bonding Interactions Using Steady-statementioning

confidence: 99%

“…[39,47] For a given hydrogen-bond donor (the acid) the strength of the hydrogen bond tends to increase with an increase in the b value of the hydrogen-bond acceptor (the base). A similar situation occurs for hydrogenbond acceptors.…”

mentioning

confidence: 99%

“…Correlation between the free energy of the proton transfer to water of phenol-like photoacids and the two bond lengths in the OÀH···O coordinates using bond-energy-bondorder theory. [39] (c): OÀH bond-length, (a): O···O separation length. The crossing points of the dotted lines indicate the bond lengths in the ground and excited states of the photoacid using the known proton-dissociation free energies of the two states in water.…”

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confidence: 99%

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Femtosecond Pump‐Probe Measurements of Solvation by Hydrogen‐Bonding Interactions

Pines

et al. 2004

ChemPhysChem

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An additional ultrafast blue shift in the transient absorption spectra of hydrogen-bonding complexes of a strong photoacid, 8-hydroxypyrene 1,3,6-trisdimethylsulfonamide (HPTA), over the solvation response of the uncomplexed HPTA and also over that of the methoxy derivative of the photoacid (MPTA) in the presence of the hydrogen-bonding base was observed on optical excitation of the photoacid. The additional 55 +/- 10 fs solvation response was found to be about 35 % and 19% of the total C(t) of HPTA in dichloromethane (DCM) when it was hydrogen-bonded to dimethylsulfoxide (DMSO) and dioxane, respectively, and about 29% of the total C(t) of HPTA in dichloroethane (DCE) when it was hydrogen-bonded to DMSO. We have assigned this additional dynamic spectral shift to a transient change in the hydrogen bond (O-H...O) that links HPTA to the complexing base, after the electronic excitation of the photoacid.

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“…Correlations between rate, equilibrium constant and free energy of proton transfer can be made [47]. Solvatochromic shifts in absorbance and emission can be analysed with the Kamlet-Taft approach [48], providing insight into the dipole moment interactions and the hydrogen bond donating and accepting capabilities of the photoacid states [38,[49][50][51][52][53].…”

Section: Photoacids As Ultrafast Optical Triggers For Proton Transfermentioning

confidence: 99%