Abstract
Electron-proton transfer (EPT) from phenols to a triplet metal-to-ligand charge transfer (MLCT)-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to inconsistent data analysis. Control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.
| Original language | English |
|---|---|
| Pages (from-to) | 4043-4048 |
| Number of pages | 6 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 8 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - Sep 7 2017 |
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ASJC Scopus subject areas
- Materials Science(all)
Cite this
Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand. / Lymar, Sergei V.; Ertem, Mehmed Z.; Lewandowska-Andralojc, Anna; Polyansky, Dmitry.
In: Journal of Physical Chemistry Letters, Vol. 8, No. 17, 07.09.2017, p. 4043-4048.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand
AU - Lymar, Sergei V.
AU - Ertem, Mehmed Z.
AU - Lewandowska-Andralojc, Anna
AU - Polyansky, Dmitry
PY - 2017/9/7
Y1 - 2017/9/7
N2 - Electron-proton transfer (EPT) from phenols to a triplet metal-to-ligand charge transfer (MLCT)-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to inconsistent data analysis. Control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.
AB - Electron-proton transfer (EPT) from phenols to a triplet metal-to-ligand charge transfer (MLCT)-excited Ru polypyridine complex containing an uncoordinated nitrogen site, 1(T), can be described by a kinetic model that accounts for the H-bonding of 1(T) to phenol, 1(T) to solvent, and phenol to solvent. The latter plays a major role in the kinetic solvent effect and commonly precludes simultaneous determination of the EPT rate constant and 1(T)-phenol H-bonding constant. A number of these quantities previously reported for similar systems are shown to be in error due to inconsistent data analysis. Control experiments replacing either 1(T) by its structural isomer with a sterically screened nitrogen site or phenol by its H-bonding surrogate, trifluoroethanol, and the observation of negative activation enthalpies for the overall reactions between 1(T) and phenols lend support to the proposed model and provide evidence for the formation of a precursor H-bonded complex between the reactants, which is a prerequisite for EPT.
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U2 - 10.1021/acs.jpclett.7b01614
DO - 10.1021/acs.jpclett.7b01614
M3 - Article
VL - 8
SP - 4043
EP - 4048
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 17
ER -