Generation and identification of 1,4-perinaphthadiyl radical cation - first observation of the electronic absorption spectrum of an ionized diradical

被引:9
作者
Zhu, ZD
Bally, T
Wirz, J
Fulscher, M
机构
[1] Univ Fribourg, Inst Phys Chem, CH-1700 Fribourg, Switzerland
[2] Univ Basel, Inst Phys Chem, CH-4056 Basel, Switzerland
[3] Chem Ctr Lund, Dept Theoret Chem, S-22100 Lund, Sweden
来源
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 | 1998年 / 05期
关键词
D O I
10.1039/a707284h
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
gamma-Irradiation of 6b,7,8,8a-tetrahydrocyclobut[a]acenaphthylene (CAN) in haloalkane glasses at 77 K yields a persistent radical cation, CAN(.+), whose electronic absorption spectrum has been obtained. Irradiation at >640 nm converts this into an isomer which is identical with that formed by ionization of 1,4-dihydro-1,4-ethanonaphtho[1,8-de][1,2]diazepine (END) and subsequent irradiation of the radical cation at lambda > 540 nm. In both cases, further irradiation at 450 nn yields the radical cation of 1,8-divinylnaphthalene (DVN.+) which was identified by ionization of DVN generated in situ by photolysis of CAN. These related observations identify the photoisomer of CAN(.+) as 1,4-perinaphthadiyl radical cation (7,8,9,10-tetrahydrocyclohepta[de] naphthalene-7,10-diylium, CND.+). [GRAPHICS] The molecular and electronic structures of all observed radical cations, as well as their electronic absorption spectra, are discussed on the basis of B3LYP and CASPT2 quantum chemical calculations and, in the case of CAN(.+) and DVN.+, also by reference to the photoelectron spectra of the neutral hydrocarbons. The CAN(.+)-->PND.+-->DVN.+ sequence of photoreactions is discussed on the basis of orbital and state correlation diagrams.
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页码:1083 / 1091
页数:9
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