Optical absorption spectra of dications of carotenoids

被引:98
作者
Jeevarajan, JA [1 ]
Wei, CC [1 ]
Jeevarajan, AS [1 ]
Kispert, LD [1 ]
机构
[1] UNIV ALABAMA,DEPT CHEM,TUSCALOOSA,AL 35487
关键词
D O I
10.1021/jp9530663
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
Quantitative optical absorption spectra of the cation radicals and the dications of canthaxanthin (I), beta-carotene (II), 7'-cyano-7'-ethoxycarbonyl-7'-apo-beta-carotene (III), and 7',7'-dimethyl-7'-apo-beta-carotene (IV) in dichloromethane solution are reported. Exclusive formation of dications occurs when the carotenoids are oxidized with ferric chloride. Addition of neutral carotenoid to the dications results in equilibrium formation of cation radicals. Oxidation with iodine in dichloromethane affords only cation radicals; electrochemical oxidation under suitable conditions yields both dications and cation radicals. Values of the optical parameters depend on the nature of the oxidative medium. The oscillator strengths calculated for gas phase cation radicals and dications of I-IV using the INDO/S method show the same trend as the experimental values.
引用
收藏
页码:5637 / 5641
页数:5
相关论文
共 32 条
[1]   INTERMEDIATE NEGLECT OF DIFFERENTIAL OVERLAP THEORY FOR TRANSITION-METAL COMPLEXES - FE, CO AND CU CHLORIDES [J].
BACON, AD ;
ZERNER, MC .
THEORETICA CHIMICA ACTA, 1979, 53 (01) :21-54
[2]   STABLE POLARONS IN POLYACETYLENE OLIGOMERS - OPTICAL-SPECTRA OF LONG POLYENE RADICAL CATIONS [J].
BALLY, T ;
ROTH, K ;
TANG, W ;
SCHROCK, RR ;
KNOLL, K ;
PARK, LY .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (07) :2440-2446
[3]  
BAUERLE P, 1993, ANGEW CHEM INT EDIT, V32, P76, DOI 10.1002/anie.199300761
[4]   BETA-CAROTENE - AN UNUSUAL TYPE OF LIPID ANTIOXIDANT [J].
BURTON, GW ;
INGOLD, KU .
SCIENCE, 1984, 224 (4649) :569-573
[5]   NATURE OF OPTICAL-TRANSITIONS IN CONJUGATED OLIGOMERS .2. THEORETICAL CHARACTERIZATION OF NEUTRAL AND DOPED OLIGOTHIOPHENES [J].
CORNIL, J ;
BELJONNE, D ;
BREDAS, JL .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (02) :842-849
[6]   NATURE OF OPTICAL-TRANSITIONS IN CONJUGATED OLIGOMERS .1. THEORETICAL CHARACTERIZATION OF NEUTRAL AND DOPED OLIGO(PHENYLENEVINYLENE)S [J].
CORNIL, J ;
BELJONNE, D ;
BREDAS, JL .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (02) :834-841
[7]   THE DEVELOPMENT AND USE OF QUANTUM-MECHANICAL MOLECULAR-MODELS .76. AM1 - A NEW GENERAL-PURPOSE QUANTUM-MECHANICAL MOLECULAR-MODEL [J].
DEWAR, MJS ;
ZOEBISCH, EG ;
HEALY, EF ;
STEWART, JJP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (13) :3902-3909
[8]   CAROTENOID CATION RADICALS PRODUCED BY THE INTERACTION OF CAROTENOIDS WITH IODINE [J].
DING, R ;
GRANT, JL ;
METZGER, RM ;
KISPERT, LD .
JOURNAL OF PHYSICAL CHEMISTRY, 1988, 92 (16) :4600-4606
[9]   DOPED BETA-CAROTENE FILMS - SPINLESS CHARGE STORAGE STABILIZED BY STRUCTURAL RELAXATION [J].
EHRENFREUND, E ;
MOSES, D ;
HEEGER, AJ ;
CORNIL, J ;
BREDAS, JL .
CHEMICAL PHYSICS LETTERS, 1992, 196 (1-2) :84-90
[10]  
FESSENDEN RW, UNPUB