TY - JOUR
T1 - Annulation of tetrathiafulvalene to the bay region of perylenediimide
T2 - Fast electron-transfer processes in polar and nonpolar solvents
AU - El-Khouly, Mohamed E.
AU - Jaggi, Michael
AU - Schmid, Belinda
AU - Blum, Carmen
AU - Liu, Shi Xia
AU - Decurtins, Silvio
AU - Ohkubo, Kei
AU - Fukuzumi, Shunichi
PY - 2011/4/28
Y1 - 2011/4/28
N2 - A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended π-conjugated molecular dyad (TTF-PDI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N′-bis(1-octylnonyl)benzoperylene-1',2':3,4:9,10-hexacarboxylic-1', 2′-anhydride-3,4:9,10-bis(imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF-PDI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the light-induced process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, π-conjugated TTF-PDI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of TTF-diamine/Ph-PDI has been observed via the triplet excited PDI for the first time.
AB - A tetrathiafulvalene donor has been annulated to the bay region of perylenediimide through a 1H-benzo[d]pyrrolo[1,2-a]imidazol-1-one spacer affording an extended π-conjugated molecular dyad (TTF-PDI). To gain insight into its ground- and excited-state electronic properties, the reference compound Ph-PDI has been prepared via a direct Schiff-base condensation of N,N′-bis(1-octylnonyl)benzoperylene-1',2':3,4:9,10-hexacarboxylic-1', 2′-anhydride-3,4:9,10-bis(imide) with benzene-1,2-diamine. Both the experimental and the computational (DFT) results indicate that TTF-PDI exhibits significant intramolecular electronic interactions giving rise to an efficient photoinduced charge-separation process. Free-energy calculations verify that the light-induced process from TTF to the singlet-excited state of PDI is exothermic in both polar and nonpolar solvents. Fast adiabatic electron-transfer processes of a compactly fused, π-conjugated TTF-PDI dyad in benzonitrile, 2-methyltetrahydrofuran, anisole and toluene were observed by femtosecond transient absorption spectral measurements. The lifetimes of radical-ion pairs slightly increase with decreasing the solvent polarities, suggesting that the charge-recombination occurs in the Marcus inverted region. By utilizing the nanosecond transient absorption technique, the intermolecular electron-transfer process in a mixture of TTF-diamine/Ph-PDI has been observed via the triplet excited PDI for the first time.
UR - http://www.scopus.com/inward/record.url?scp=79955384669&partnerID=8YFLogxK
U2 - 10.1021/jp2007667
DO - 10.1021/jp2007667
M3 - Article
AN - SCOPUS:79955384669
SN - 1932-7447
VL - 115
SP - 8325
EP - 8334
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 16
ER -