+ Site Statistics
References:
54,258,434
Abstracts:
29,560,870
PMIDs:
28,072,757
+ Search Articles
+ PDF Full Text Service
How our service works
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ Translate
+ Recently Requested

Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand



Role of Hydrogen Bonding in Photoinduced Electron-Proton Transfer from Phenols to a Polypyridine Ru Complex with a Proton-Accepting Ligand



Journal of Physical Chemistry Letters 8(17): 4043-4048



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.

Please choose payment method:






(PDF emailed within 0-6 h: $19.90)

Accession: 060216221

Download citation: RISBibTeXText

PMID: 28792768

DOI: 10.1021/acs.jpclett.7b01614


Related references

Solvent-dependent transition from concerted electron-proton to proton transfer in photoinduced reactions between phenols and polypyridine Ru complexes with proton-accepting sites. Dalton Transactions 47(44): 15917-15928, 2018

Hydrogen bonding between hydroxylic donors and MLCT-excited Ru(bpy) 2 (bpz) 2+ complex: implications for photoinduced electron-proton transfer. Chemical Communications 2019, 2019

Photoinduced proton-coupled electron transfer of hydrogen-bonded p-nitrophenylphenol-methylamine complex in solution. Journal of Physical Chemistry. B 117(1): 316-325, 2013

Proton Quantization and Vibrational Relaxation in Nonadiabatic Dynamics of Photoinduced Proton-Coupled Electron Transfer in a Solvated Phenol-Amine Complex. Journal of Physical Chemistry. B 120(9): 2407-2417, 2016

Protonation of naphthalene proton sponges containing higher N-alkyl groups Structural consequences on proton accepting properties and intramolecular hydrogen bonding. Journal of Molecular Structure 892(1-3): 63-67, 2008

Hydrogen bonding to carbonyl hydride complex Cp*Mo(PMe(3))(2)(CO)H and its role in proton transfer. Dalton Transactions 39(8): 2008-2015, 2010

Photoinduced Generation of Long-Lived Proton Transfer States: Photoinduced Proton Transfer from 2-(2,4-Dinitrobenzyl)pyridine to a Proton Cage, the [2.1.1] Cryptand. The Journal of Physical Chemistry A 101(37): 6850-6854, 1997

DFT/B3LYP study of the substituent effect on the reaction enthalpies of the individual steps of single electron transfer-proton transfer and sequential proton loss electron transfer mechanisms of phenols antioxidant action. Journal of Physical Chemistry. a 110(44): 12312-12320, 2006

A biomimetic model of the electron transfer in photosystem II - photoinduced electron transfer reactions of ruthenium (II)-polypyridine complexes with phenols. Photo/electrochemistry and photobiology in the environment, energy and fuel: 169-206, 2006

Electrocatalytic Hydrogen Production by an Aluminum(III) Complex: Ligand-Based Proton and Electron Transfer. Angewandte Chemie 54(40): 11642-6, 2015

Hydrogen bonding and proton transfer between nitro-phenols and lecithin in apolar solvents. Chemistry and Physics of Lipids 30(1): 93-100, 1982

Hydrogen bonding and proton transfer between nitro phenols and lecithin in apolar solvents. Chemistry & Physics of Lipids 30(1): 93-100, 1982

Role of Solvent Dynamics in Photoinduced Proton-Coupled Electron Transfer in a Phenol-Amine Complex in Solution. Journal of Physical Chemistry Letters 6(18): 3515-3520, 2015

Hydrogen transfer between sulfuric acid and hydroxyl radical in the gas phase: competition among hydrogen atom transfer, proton-coupled electron-transfer, and double proton transfer. Journal of Physical Chemistry. a 110(5): 1982-1990, 2006

Proton-Coupled Electron-Transfer Processes in Ultrafast Time Domain: Evidence for Effects of Hydrogen-Bond Stabilization on Photoinduced Electron Transfer. Chemistry 23(14): 3455-3465, 2017