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Analysis of Hydroge...
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Dongare, PrateekUppsala universitet,Fysikalisk kemi,Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA.
(author)
Analysis of Hydrogen-Bonding Effects on Excited-State Proton-Coupled Electron Transfer from a Series of Phenols to a Re(I) Polypyridyl Complex
- Article/chapterEnglish2017
Publisher, publication year, extent ...
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2017-06-01
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AMER CHEMICAL SOC,2017
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printrdacarrier
Numbers
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LIBRIS-ID:oai:DiVA.org:uu-329668
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https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-329668URI
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https://doi.org/10.1021/acs.jpcc.7b02449DOI
Supplementary language notes
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Language:English
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Summary in:English
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Subject category:ref swepub-contenttype
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Subject category:art swepub-publicationtype
Notes
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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.
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Bonn, Annabell G.Uppsala universitet,Fysikalisk kemi,Univ North Carolina Chapel Hill, Dept Chem, Chapel Hill, NC 27599 USA.(Swepub:uu)annbo173
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Maji, SomnathUppsala universitet,Fysikalisk kemi,Indian Inst Technol, Dept Chem, Hyderabad 502285, Telangana, India.
(author)
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Hammarström, Leif,1964-Uppsala universitet,Fysikalisk kemi(Swepub:uu)leifhamm
(author)
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Uppsala universitetFysikalisk kemi
(creator_code:org_t)
Related titles
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In:The Journal of Physical Chemistry C: AMER CHEMICAL SOC121:23, s. 12569-125761932-74471932-7455
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