TY - GEN
T1 - Photoinduced electron-transfer in 2-tert-butyl-3-(anthracen-9-yl)-2,3- diazabicyclo[2.2.2]octane
AU - Valverde-Aguilar, Guadalupe
AU - Garcia-Macedo, Jorge
AU - Wang, Xianghuai
AU - Zink, Jeffrey I.
AU - Nelsen, Stephen F.
PY - 2006
Y1 - 2006
N2 - Intramolecular photoinduced electron-transfer from a hydrazine unit to an aromatic group is studied by resonance Raman spectroscopy and electronic absorption spectroscopy. Substituted hydrazine functional groups have played an important role in studies of electron transfer reactions, photo-induced intramolecular electron transfer, and of mixed valence. A prototypical compound, 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane, that has the hydrazine to anthracene charge transfer band in a region of the visible spectrum suitable for detailed resonance Raman spectroscopy is studied in detail. Excitation profiles are obtained, calculated quantitatively by using time-dependent theoretical methods, and interpreted with the assistance of molecular orbital calculations. Excited state distortions are calculated. The largest distortions occur on the hydrazine unit; the normal mode showing the largest distortion (659 cm -1, calculated at 665 cm -1) involves an out of plane C-N-N-C bend consistent with removing an electron from the NN n antibonding orbital. Anthracene ring-centered CC stretches also are enhanced, consistent with populating an antibonding n orbital centered on the ring. Excellent fits to all of the excitation profiles and to the absorption band are obtained using one set of excited state potential surfaces.
AB - Intramolecular photoinduced electron-transfer from a hydrazine unit to an aromatic group is studied by resonance Raman spectroscopy and electronic absorption spectroscopy. Substituted hydrazine functional groups have played an important role in studies of electron transfer reactions, photo-induced intramolecular electron transfer, and of mixed valence. A prototypical compound, 2-tert-Butyl-3-(Anthracen-9-yl)-2,3-Diazabicyclo[2.2.2]octane, that has the hydrazine to anthracene charge transfer band in a region of the visible spectrum suitable for detailed resonance Raman spectroscopy is studied in detail. Excitation profiles are obtained, calculated quantitatively by using time-dependent theoretical methods, and interpreted with the assistance of molecular orbital calculations. Excited state distortions are calculated. The largest distortions occur on the hydrazine unit; the normal mode showing the largest distortion (659 cm -1, calculated at 665 cm -1) involves an out of plane C-N-N-C bend consistent with removing an electron from the NN n antibonding orbital. Anthracene ring-centered CC stretches also are enhanced, consistent with populating an antibonding n orbital centered on the ring. Excellent fits to all of the excitation profiles and to the absorption band are obtained using one set of excited state potential surfaces.
KW - Absorption
KW - Electron-transfer
KW - Mixed valence
KW - Raman spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=33751093793&partnerID=8YFLogxK
U2 - 10.1117/12.680904
DO - 10.1117/12.680904
M3 - Contribución a la conferencia
AN - SCOPUS:33751093793
SN - 0819464007
SN - 9780819464002
T3 - Proceedings of SPIE - The International Society for Optical Engineering
BT - Nanophotonic Materials III
T2 - Nanophotonic Materials III
Y2 - 13 August 2006 through 14 August 2006
ER -