S1 and S2 states of apo- and diapocarotenes

被引:67
作者
Christensen, RL [1 ]
Goyette, M
Gallagher, L
Duncan, J
DeCoster, B
Lugtenburg, J
Jansen, FJ
van der Hoef, I
机构
[1] Bowdoin Coll, Dept Chem, Brunswick, ME 04011 USA
[2] Leiden Univ, Gorlaeus Labs, NL-2300 RA Leiden, Netherlands
关键词
D O I
10.1021/jp983946s
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A series of apocarotenes with 5 to 11 conjugated double bonds were synthesized and all-trans isomers were isolated using HPLC techniques. Absorption, fluorescence, and fluorescence excitation spectra were obtained in 77 K glasses. As previously noted for other polyenes and carotenoids, fluorescence spectra of the apocarotenes exhibit a systematic crossover from S-1(2(1)A(g)) --> S-0(l(1)A(g)) to S-2(2(1)A(g)) --> S-0(1(1)A(g)) emissions and a sharp decrease in fluorescence yields with increasing conjugation, The apocarotene spectra have sufficient resolution to accurately locate the dominant vibronic bands of the S-0(1(1)A(g)) --> S-2(1(1)B(u)) and S-1(2(1)A(g)) --> S-0(1(1)A(g)) transitions, thus leading to an accurate catalog of S-1 and S-2 electronic energies as a function of conjugation length. We also have obtained the low-temperature absorption and fluorescence spectra of several model polyenes and diapocarotenes. Comparisons between these series allow a systematic exploration of the influence of terminal cyclohexenyl rings on the energies of carotenoid S-1 and S-2 states. In addition, these preliminary studies indicate that the nature of the terminal double bond has a significant influence on nonradiative decay processes in longer carotenoid systems. Implications regarding the use of energy gap law extrapolations to estimate the 2(1)A(g) energies of long carotenoids are discussed.
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页码:2399 / 2407
页数:9
相关论文
共 61 条
[1]   Excitation energy transfer in carotenoid-chlorophyll protein complexes probed by femtosecond fluorescence decays [J].
Akimoto, S ;
Takaichi, S ;
Ogata, T ;
Nishimura, Y ;
Yamazaki, I ;
Mimuro, M .
CHEMICAL PHYSICS LETTERS, 1996, 260 (1-2) :147-152
[2]   DUAL SINGLET-STATE EMISSION IN A SERIES OF MINI-CAROTENES [J].
ANDERSSON, PO ;
GILLBRO, T ;
ASATO, AE ;
LIU, RSH .
JOURNAL OF LUMINESCENCE, 1992, 51 (1-3) :11-20
[3]   SOLVENT AND TEMPERATURE EFFECTS ON DUAL FLUORESCENCE IN A SERIES OF CAROTENES - ENERGY-GAP DEPENDENCE OF THE INTERNAL-CONVERSION RATE [J].
ANDERSSON, PO ;
BACHILO, SM ;
CHEN, RL ;
GILLBRO, T .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (44) :16199-16209
[4]   POLYENE SPECTROSCOPY - VIBRONIC EVIDENCE FOR A FORBIDDEN TRANSITION IN DECA-2,4,6,8-TETRAENE [J].
ANDREWS, JR ;
HUDSON, BS .
CHEMICAL PHYSICS LETTERS, 1978, 57 (04) :600-604
[5]   Excited state energies and internal conversion in diphenylpolyenes: from diphenylbutadiene to diphenyltetradecaheptaene [J].
Bachilo, SM ;
Spangler, CW ;
Gillbro, T .
CHEMICAL PHYSICS LETTERS, 1998, 283 (3-4) :235-242
[6]  
BIRGE RR, 1990, BIOCHIM BIOPHYS ACTA, V293, P1016
[7]   FLUORESCENCE FROM THE S(1)(2(1)AG) STATE OF ALL-TRANS-BETA-CAROTENE [J].
BONDAREV, SL ;
KNYUKSHTO, VN .
CHEMICAL PHYSICS LETTERS, 1994, 225 (4-6) :346-350
[8]   FLUORESCENCE OF GASEOUS TETRAENES AND PENTAENES [J].
BOUWMAN, WG ;
JONES, AC ;
PHILLIPS, D ;
THIBODEAU, P ;
FRIEL, C ;
CHRISTENSEN, RL .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (19) :7429-7434
[9]   THE 2(1)A(G) STATE OF ISOLATED CIS,TRANS-1,3,5,7-OCTATETRAENE - 2-COLOR RESONANCE ENHANCED 2-PHOTON IONIZATION STUDIES [J].
BUMA, WJ ;
KOHLER, BE ;
SHALER, TA .
JOURNAL OF CHEMICAL PHYSICS, 1992, 96 (01) :399-407
[10]  
CHOI YS, 1994, J CHEM PHYS, V100, P9629