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 1²⁺−4²⁺ 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.