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, (EE)-1,4-bis[4-{bis(4-methoxyphenyl)amino}styryl]benzene, 2, and two longer homologues, (E,EE)-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]styry)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 21 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-[4-14-(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.