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.

45 000 Elektronen pro Molekül und Sekunde – ein solcher Stromfluss wurde an einem Langmuir‐Blodgett‐Film der D+‐π‐A−‐Verbindung 1 zwischen oxidfreien Goldelektroden beobachtet. Bei 2.2 V betrug das Verhältnis der Ströme in Fluss‐ und Sperrrichtung 5.38.

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.