| A series of 9-bond-bridged protected tetraalkyl (9-(9-azabicyclo[3.3.1]-3-one) aryl diamine radical cations, which are linked between the o,o'-position of a bezidine framework, were made and studied. These compounds are delocalized intervalence compounds. Even though Marcus-Hush two-state model is good enough for some delocalized compounds, it is inadequate for consideration of the optical spectra of these compounds. The Neighboring Orbital Model was developed and used to discuss the optical spectra of these compounds.;The radical cations of 2,3-Diaryl-2,3-diazabicyclo[2.2.2]octanes, 22/Ar2(X), the delocalized symmetrical intervalence compounds, and their tert-butyl monoaryl analogues, 22/tBuAr(X) were made and used to study the electronic interactions. The Neighboring Orbital Model was used for this discussion.;The radical cations of acyclic, monocyclic diaryl and tetraaryl hydrazine derivatives were made. The optical spectra of radical cations of acyclic diaryl hydrazine derivatives have the typical characterizations of delocalized compounds. The optical spectra of radical cations of monocyclic diaryl hydrazine derivatives have the similar characterizations of the optical spectra of radical cations of 2,3-Diaryl-2,3-diazabicyclo[2.2.2]octaves. The optical spectra of cations of tetraaryl hydrazine derivatives have their own specific characteristics.;The optical spectra of 11-bond-bridged diaminophenyl-centered radical cations that have two atom bridges of C≡C, C=C, and N=N, which are also delocalized intervalence compounds, have been studied using the Neighboring Orbital Model.;The 10-bond-bridged diaminophenyl-centered radical cations that have one saturated atom bridges of O, S, CMe2, SiPh2, SiMe 2 and one unsaturated carbon bridges of C=O, C=S, C=CMe2, C=cHx, C=CPh2, C=FL, C=NNcHp were made and studied. The cations that have one saturated atom bridges of O, S, CMe2 and the cations that have one unsaturated carbon bridges of C=CPh2, C=FL are localized intervalence compounds, other else compounds are not stable enough to test. |
