Intramolecular Energy Transfer to trans -Stilbene †. Schanze, K. S, Lucia, L. A, Cooper, M., Walters, K. A, Ji, H., & Sabina, O. Journal of Physical Chemistry A, 102(28):5577–5584, July, 1998.
Intramolecular Energy Transfer to trans -Stilbene † [link]Paper  doi  abstract   bibtex   
This study examines the photophysics of a series of transition-metal complexes that contain a (diimine)ReI(CO)3(py) chromophore covalently linked to trans-stilbene via a semirigid amide spacer. In this series of complexes moderately exothermic triplet-triplet energy transfer from the 3dp* charge-transfer excited state of the diimine-Re chromophore to trans-stilbene is competitive with normal radiative and nonradiative decay of the 3dp* state. The rate const. for intramol. energy transfer (kEnT) was detd. as a function of temp. from 190 to 290 K for three complexes in which the driving force (DEEnT) varies from ca. -29 to -38 kJ mol-1. The temp.-dependence data indicate that energy transfer is characterized by a low activation energy (Ea ?2 kJ mol-1) and a low-frequency factor (A ̃106 s-1). The results are interpreted by a mechanism in which energy transfer from the 3dp* state to trans-stilbene occurs at nearly the optimal driving force (i.e., DEEnT ̃l, where l is the reorganization energy). However, owing to the moderate sepn. distance between the Re(I) center and trans-stilbene, the exchange coupling matrix element (VTT) is small, leading to low A values. [on SciFinder (R)]
@article{Schanze1998d,
abstract = {This study examines the photophysics of a series of transition-metal complexes that contain a (diimine)ReI(CO)3(py) chromophore covalently linked to trans-stilbene via a semirigid amide spacer. In this series of complexes moderately exothermic triplet-triplet energy transfer from the 3dp* charge-transfer excited state of the diimine-Re chromophore to trans-stilbene is competitive with normal radiative and nonradiative decay of the 3dp* state. The rate const. for intramol. energy transfer (kEnT) was detd. as a function of temp. from 190 to 290 K for three complexes in which the driving force (DEEnT) varies from ca. -29 to -38 kJ mol-1. The temp.-dependence data indicate that energy transfer is characterized by a low activation energy (Ea ?2 kJ mol-1) and a low-frequency factor (A \~{}106 s-1). The results are interpreted by a mechanism in which energy transfer from the 3dp* state to trans-stilbene occurs at nearly the optimal driving force (i.e., DEEnT \~{}l, where l is the reorganization energy). However, owing to the moderate sepn. distance between the Re(I) center and trans-stilbene, the exchange coupling matrix element (VTT) is small, leading to low A values. [on SciFinder (R)]},
annote = {From Duplicate 1 ( },
author = {Schanze, Kirk S and Lucia, Lucian A and Cooper, Megan and Walters, Keith A and Ji, Hai-feng and Sabina, Osvaldo},
doi = {10.1021/jp980203y},
file = {:C$\backslash$:/Users/walterske/SkyDrive/References/Journal of Physical Chemistry A/1998 - Schanze et al. - Intramolecular Energy Transfer to trans -Stilbene †.pdf:pdf},
issn = {1089-5639},
journal = {Journal of Physical Chemistry A},
keywords = {Intramolecular energy transfer (triplet-triplet,Physical process kinetics (of intramol. triplet-tr,intramol triplet energy transfer kinetics tricarbo,to trans-stilbene in tricarbonyldiiminepyridinesti},
month = jul,
number = {28},
pages = {5577--5584},
title = {{Intramolecular Energy Transfer to trans -Stilbene †}},
url = {http://pubs.acs.org/cgi-bin/archive.cgi/jpcafh/1998/102/i28/html/jp980203y.html http://pubs.acs.org/doi/abs/10.1021/jp980203y},
volume = {102},
year = {1998}
}

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