Intervalence transitions in the mixed-valence monocations of bis(triarylamines) linked with vinylene and phenylene-vinylene bridges.

(E)-4,4'-Bis[bis(4-methoxyphenyl)amino]stilbene, 1, (E,E)-1,4-bis[4-[bis(4-methoxyphenyl)amino]styryl]benzene, 2, and two longer homologues, (E,E,E)-4,4'-bis[4-[bis(4-methoxyphenyl)amino]styryl]stilbene, 3, and (E,E,E,E)-1,4-bis(4-[4-[bis(4-methoxyphenyl)amino]styryl]styryl)benzene, 4, have been oxidized to their mono- and dications using tris(4-bromophenyl)aminium hexachloroantimonate. The intervalence charge-transfer (IVCT) band of 1(+) is narrow and asymmetric and exhibits only weak solvatochromism. Analysis of this band indicates that 1(+) is a class-III or class-II/III borderline mixed-valence species. In contrast, a broad, strongly solvatochromic IVCT band is observed for 2(+), indicating that this species is a class-II mixed-valence species. The assignment of 1(+ ) and 2(+) as symmetric class-III and unsymmetric class-II species, respectively, is also supported by AM1 calculations. Hush analysis of the IVCT bands of both 1(+) and 2(+) gives larger electronic couplings, V, than for their analogues in which the double bonds are replaced with triple bonds. The diabatic electron-transfer distance, R, in 1(+) can be estimated by comparison of the V estimated by Hush analysis and from the IVCT maximum; it is considerably less than the geometric N-N separation, a result supported by quantum-chemical estimates of R for 1(+)-4(+). In 3(+) and 4(+), the IVCT is largely obscured by an intense absorption similar to a band seen in the corresponding dications and to that observed in the monocation of a model compound, (E,E,E)-1-[bis(4-methoxyphenyl)amino]-4-[4-[4-(4-tert-butylstyryl)styryl]styryl]benzene, 5, containing only one nitrogen redox center; we attribute this band to a bridge-to-N(+) transition. The corresponding dications 1(2+)-4(2+) show a complementary trend in the coupling between redox centers: the shortest species is diamagnetic, while the dication with the longest bridge behaves as two essentially noninteracting radical centers.