Macroscopic and nanoscopic current−voltage measurements reveal asymmetries in the DC electrical conductivity through Langmuir−Blodgett multilayers and even monolayers of γ-(n-hexadecyl)quinolinum tricyanoquinodimethanide, C16H33Q-3CNQ (5). These asymmetries are due to a transition of the ground-state zwitterion to an excited-state conformer which is probably neutral. Unimolecular electrical rectification by monolayers of 5 is unequivocally confirmed.

Hexadecylquinolinium tricyanoquinodimethanide (1), a unimolecular rectifier of electrical current with a large ground-state dipole moment (43 ± 8 D), reveals large hypsochromic shifts of the absorption spectrum. Two fluorescent emissions were observed:  one in the visible region (quantum yield φ ≈ 0.01, not solvatochromic) and one in the near-infrared spectrum (weakly solvatochromic). Using a prolate spheroidal cavity model and the absorption maxima measured in eight solvents, the excited-state dipole moment of 1 is estimated as 8.7 D. The NMR spectral lines broaden above 330 K and lose the multiplet structure. The core-level N 1s XPS spectrum reveals the three expected N valence states. The valence-level XPS spectrum can be correlated with theory. Simultaneous cyclic voltammetry and electron spin resonance of the radical anion of 1 shows that the spin density in the LUMO of 1 is concentrated on the tricyanoquinodimethanide portion of the anion. The molecule is clearly zwitterionic in the ground state, both in LB films and in solution, and is undissociated (“neutral”) in its first excited state.

Amine-based donor radicals, such as dimethylamino-, diethylamino-and morpholinonitronyl nitroxides, were synthesized, and their donor abilities were examined by cyclic voltammetry. ESR spectra of the singly oxidized donor radicals showed ground state triplet signals derived from the cation radicals of these donor radicals. The result was interpreted by the presence of the ferromagnetic coupling between the generated π-spin and the localized unpaired electron on the radical unit. According to the molecular orbital calculations, the ferromagnetic coupling between these two spins is originated from the space-sharing nature between SOMO which is localized on the radical unit and SOMO′ which is derived from HOMO of the donor radical upon one-electron oxidation. Therefore, the cation-radicals of these donor radicals can be regarded as a heteroanalogue of trimethylenemethane. p-and m-dimethylaminophenyl nitronyl nitroxides were synthesized in order to expand the π-electronic structure of the donor unit, and the singly oxidized species were also found to afford triplet ESR signals. The origin of the ferromagnetic coupling of these aminophenyl nitronyl nitroxides was discussed on the same basis. Charge transfer complexes of some of the donor radicals with chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were prepared, and the conducting and magnetic properties were examined.