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Analysis of Hydrogen-Bonding Effects on Excited-State Proton-Coupled Electron Transfer from a Series of Phenols to a Re(I) Polypyridyl Complex
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström. Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström. Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström. Indian Inst Technol, Dept Chem, Hyderabad 502285, Telangana, India..
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.
2017 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 23, 12569-12576 p.Article in journal (Refereed) Published
Abstract [en]

In the present study of proton-coupled electron transfer (PCET) reactions, the excited-state of a fac-[(CO)(3)Re-I(bpy)(4,4'-bpy)](+) (bpy = 2,2'-bipyridine and 4,4'-bpy = 4,4'-bipyridine) complex was reductively quenched by a series of phenols. A variation of substituents on the phenols substantially alters their pK(a) and E degrees values and provides an opportunity to study photoinduced PCET as a function of their redox properties. Analyses of absorption spectral changes indicate that the phenols form a weak hydrogen bond with the pyridinic nitrogen of the 4,4'-bpy ligand in the ground-state, and ground-state association, constant (K-A) values were determined. This H-bonded adduct quenches the excited Re complex by PCET from the phenol, to form the reduced and,protonated Re complex. The KA values-obtained aid quantitative evaluation of the rate constant for the PCET reaction in the H-bonded, adduct. Thus, photophysical studies and Mechanistic analysis indicate that the reaction occurs via a concerted mechanistic pathway, for the unsubstituted phenol and phenols with electron-withdrawing subtituents. Furthermore; the magnitude of the quenching varies systematically with the proton-coupled potentials of the phenols and not their hydrogen-bonding strength (as reflected in K-A). This study is one of the first detailed analyses of intermolecular H-bonding between a self-assembling metal complex and a series of substituted phenols in an effort to study their relationship with the kinetic parameters in a photoinduced CPET reaction.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2017. Vol. 121, no 23, 12569-12576 p.
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-329668DOI: 10.1021/acs.jpcc.7b02449ISI: 000403731700007OAI: oai:DiVA.org:uu-329668DiVA: diva2:1142692
Funder
Swedish Research Council, 2016-04271Swedish Energy Agency, 11674-5Knut and Alice Wallenberg Foundation, 2011.0067
Available from: 2017-09-20 Created: 2017-09-20 Last updated: 2017-09-20Bibliographically approved

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