ELECTRONIC ABSORPTION-SPECTROSCOPY OF SOME EXCEPTIONALLY STABLE 1,4-DIALKYL-1,4-DIHYDRO-1,4-DIAZINIUM RADICAL CATIONS - ASSIGNMENT OF TRANSITIONS, VIBRATIONAL STRUCTURE AND EFFECTS OF PI-PI DIMERIZATION

被引:20
作者
HILGERS, F [1 ]
KAIM, W [1 ]
SCHULZ, A [1 ]
ZALIS, S [1 ]
机构
[1] CZECHOSLOVAK ACAD SCI,J HEYROVSKY INST PHYS CHEM & ELECTROCHEM,CZ-18223 PRAGUE,CZECH REPUBLIC
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1994年 / 01期
关键词
D O I
10.1039/p29940000135
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
UV-VIS Absorption spectroscopy of the unusually stable and structurally characterized radical cations 1,4-diethyl-1,4-dihydropyrazinium (1.+), 1,4-diethyl-1,4-dihydroquinoxalinium monomer (2,+) and pi-pi dimer [(2.+)2], 1,4,6,7-tetramethyl-1,4-dihydroquinoxalinium (3.+) and 5,10-diethyl-5,10-dihydrophenazinium (4.+) reveals low-energy pi-->pi* transitions with different intensities and partial vibrational structuring. The spectra of the radical cations and of the corresponding dications (1(2+)-4(2+)) have been analysed with the help of INDO/S calculations; the resulting assignments could also be rationalized using Huckel MO theory. Both higher symmetric systems 1.+ and 4.+ exhibit vibrationally split long-wavelength bands. The additional long-wavelength absorption of the pi-pi dimer (2.+)2 (K(D) ca. 4 X 10(3)) is assigned to a charge transfer transition, similar to that of methylviologen radical dimer.
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页码:135 / 138
页数:4
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