ELECTRONIC-ENERGY LEVELS IN A HOMOLOGOUS SERIES OF UNSUBSTITUTED LINEAR POLYENES
ELECTRONIC-ENERGY LEVELS IN A HOMOLOGOUS SERIES OF UNSUBSTITUTED LINEAR POLYENES
复制标题
DOI：
10.1021/ja00526a003
复制
发表时间：
1980-01-01
影响因子：
15
通讯作者：
CHRISTENSEN, RL
中科院分区：
文献类型：
--
作者：
DAMICO, KL;MANOS, C;CHRISTENSEN, RL
得到了1,3,5,7 -辛四烯、1,3,5,7,9 -癸五烯和1,3,5,7,9,11 -十二十六烯在室温溶液和77 K玻璃中的吸收、发射和激发光谱。所有光谱都表现出在强允许吸收（'Ag-*'Bu）和荧光（'Ag*-* 1 Ag）起源之间的特征间隙。与先前甲基取代多烯的结果比较表明，‘ bu -’Ag*能隙是取代度的敏感函数。溶剂效应研究已被用来推断未取代的多烯到气相条件下的转变能。对于四烯、五烯和六烯，bu -1 Ag*的能差分别为6380、7050和7420 cm-1。根据现有的多烯电子态理论描述，对这些结果进行了讨论。
Absorption, emission, and excitation spectra of 1, 3, 5, 7-octatetraene, 1, 3, 5, 7, 9-decapentaene, and 1, 3, 5, 7, 9, 11-dodecahexaene have been obtained in room temperature solutions and 77 K glasses. All spectra exhibit the characteristic gap between the origin of the strongly allowed absorption ('Ag-*'Bu) and the origin of fluorescence ('Ag*-* 1 Ag). Comparison with results previously obtained for methyl-substituted polyenes shows that the'Bu-'Ag* energy gap is a sensitive functionof the degree of substitution. Solvent-effectstudies have been used to extrapolate transition energies of the unsubstituted polyenes to gas-phase conditions. For the tetraene, pentaene, and hexaene the'Bu-1 Ag* energy differences are 6380, 7050, and 7420 cm-1, respectively. These results are discussed in terms of current theoretical descriptions of polyene electronic states.