TY - JOUR
T1 - Kinetics and mechanism of intramolecular electron transfer in solution
AU - Huppert, Dan
AU - Kanety, Hannah
AU - Kosower, Edward M.
N1 - Funding Information:
In summary, intramolecular electron-transfer reactions are controlled by solvent molecule diffusion or by local group motion. D. H. thanks the Binational Science Foundation for support. We also thank R. Bersohn, M. Bixon, J. Jortner and G. Navon for helpful discussions. E. M. Kosower and K. Tanizawa, Chem. Phys. Lett., 1972,16,419. E. M. Kosower, H. Dodiuk, K. Tanizawa, M. Ottolenghi and N. Orbach, J. Am. Chem. SOC., 1975,97, 2167. H. Dodiuk and E. M. Kosower, J. Phys. Chem., 1977, 81, 50. E. M. Kosower and H. Dodiuk, J. Am. Chem. SOC., 1978, 100,4173. E. M. Kosower, H. Dodiuk and H. Kanety, J. Am. Chem. Soc., 1978, 100, 4179.
PY - 1982
Y1 - 1982
N2 - The picosecond pulse generated S1,np state of 6-N-4-methylphenylamino-2-naphthalenesulphonic acid NN-dimethylamide (TNSDMA) decays by intramolecular electron transfer (i.e.t) faster than the appearance of the product, an equilibrium mixture of the charge-transfer, S1,ct, and S1,np states (temperature-independent ratio of 4-5), which decays at ca. 0.1 of the rate for the S1,np state. In propan-1-ol, rates of "fast" i.e.t. processes vary with solvent cluster motion (1/τ1, lowest dielectric relaxation rate) over a wide range of temperatures with log k linear in 2/3 log (1/η). Up to ca. -15°C, "slow" i.e.t. processes probably vary in the same way, but at higher temperatures they are controlled by local group motion (1/τ2, second lowest dielectric relaxation rate). A molecular model for the S 1,ct -state-methanol complex is presented.
AB - The picosecond pulse generated S1,np state of 6-N-4-methylphenylamino-2-naphthalenesulphonic acid NN-dimethylamide (TNSDMA) decays by intramolecular electron transfer (i.e.t) faster than the appearance of the product, an equilibrium mixture of the charge-transfer, S1,ct, and S1,np states (temperature-independent ratio of 4-5), which decays at ca. 0.1 of the rate for the S1,np state. In propan-1-ol, rates of "fast" i.e.t. processes vary with solvent cluster motion (1/τ1, lowest dielectric relaxation rate) over a wide range of temperatures with log k linear in 2/3 log (1/η). Up to ca. -15°C, "slow" i.e.t. processes probably vary in the same way, but at higher temperatures they are controlled by local group motion (1/τ2, second lowest dielectric relaxation rate). A molecular model for the S 1,ct -state-methanol complex is presented.
UR - http://www.scopus.com/inward/record.url?scp=33748407532&partnerID=8YFLogxK
U2 - 10.1039/DC9827400161
DO - 10.1039/DC9827400161
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AN - SCOPUS:33748407532
SN - 0301-7249
VL - 74
SP - 161
EP - 175
JO - Faraday Discussions of the Chemical Society
JF - Faraday Discussions of the Chemical Society
ER -