Electronic energy levels in all-trans long linear polyenes:: The case of the 3,20-di(tert-butyl)-2,2,21,21-tetramethyl-all-trans-3,5,7,9,11,13,15,17,19-docosanonaen (ttbp9) conforming to Kasha's rule

被引:15
作者
Catalán, J
Hopf, H
Mlynek, C
Klein, D
Kilickiran, P
机构
[1] Univ Autonoma Madrid, Dept Quim Fis Aplicada, Fac Ciencias C II 203, E-28049 Madrid, Spain
[2] Tech Univ Braunschweig, Inst Organ Chem, D-38106 Braunschweig, Germany
关键词
absorption; fluorescence spectroscopy; Kasha's rule photochemistry; polyenes;
D O I
10.1002/chem.200401093
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The absorption, fluorescence and fluorescence excitation spectra for 3,20-di(tert-butyl)-2,2,21,21-tetrameth- yl-all-trans-3,5,7,9,11,13,15,17,19-doco-sanonaen (ttbP9) in dilute solutions of 2-methylbutane were recorded at temperatures over the range 120-280 K. The high photostability of this nonaene allows us to assert that it exhibits a single fluorescence and that this can be unequivocally assigned to emission from its 1(1)B(u) excited state, it being the first excited electronic state. Available photophysical data for this polyene and the wealth of information reported for shorter all-trans polyenes allow us to conclude that if the first excited electronic state for the chromophore possessed 2(1)A(g) symmetry, then the energy of such a state might have been so close to that of the 1(1)B(u), state that: 1) the radiationless internal conversion mechanism would preclude the observation of the emission from the 1(1)B(u) state reported in this work and 2) the 2(1)A(g) state reached through internal conversion would be vibrationally coupled to 1(1)B(u), and would facilitate the detection of the emission from 2(1)A(g), which was not observed in any of the solvents used in this work. The spectroscopic and photochemical implications of these findings for other polyenes are discussed.
引用
收藏
页码:3915 / 3920
页数:6
相关论文
共 28 条
[1]  
ABRAHAMSON SE, 1967, PROGR BIOPHYSICIS MO, V7
[2]   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
[3]   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
[4]  
BERLMAN IB, 1974, J PHYS CHEM, V74, P3085
[5]   RELATIONS BETWEEN FLUORESCENCE AND ABSORPTION PROPERTIES OF ORGANIC MOLECULES [J].
BIRKS, JB ;
DYSON, DJ .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL AND PHYSICAL SCIENCES, 1963, 275 (1360) :135-+
[6]  
BOWMAN WG, 2000, J PHYS CHEM-US, V94, P7429
[7]   Empirical treatment of the inductive and dispersive components of solute-solvent interactions:: the Tolvent polarizability (SP) scale [J].
Catalán, J ;
Hopf, H .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2004, 2004 (22) :4694-4702
[8]   On the ordering of the first two excited electronic states in all-trans linear polyenes [J].
Catalán, J ;
de Paz, JLG .
JOURNAL OF CHEMICAL PHYSICS, 2004, 120 (04) :1864-1872
[9]   On the inversion of the 1 Bu and 2 Ag electronic states in α,ω-diphenylpolyenes [J].
Catalán, J .
JOURNAL OF CHEMICAL PHYSICS, 2003, 119 (03) :1373-1385
[10]   HIGH-RESOLUTION OPTICAL SPECTROSCOPY OF POLYENES RELATED TO VISUAL CHROMOPHORE [J].
CHRISTENSEN, RL ;
KOHLER, BE .
JOURNAL OF PHYSICAL CHEMISTRY, 1976, 80 (20) :2197-2200