From the results of polarized absorption spectra and MO calculations, the electronic structures of
p-diethylamino and
p-nitro substituted benzenediazonium cations (The unsubstituted cation is abbreviated to BAF, and the
p-diethylamino and
p-nitro substituted cations to
p-BAF-N (C
2H
5)
2 and
p-BAF-NO
2, respectively.) have been discussed. The first and second excited states wavefunctions (Ψ
01 and Ψ
02) of BAF belong to
1B2 and
1A
1 (
C2υ pdint group), respectively. The first excited state wavefunction (Ψ
1) of
p-BAF-NO
2 is a type of
1B
2 symmetry and corresponds to Ψ
01 of BAF, while Ψ
1, of
p-BAF-N (C
2H
5)
2 is of
1A
1 symmetry and corresponds to Ψ
02 of BAF, i, e., the origin of the first singlet excited state of
p-BAF-NO
2 is quite different from that of
p-BAF-N (C
2H
5)
2. The differences in the photochemical reactivities in both compounds may be attributable to the differences in the nature of the first excited states.
抄録全体を表示