Attempts to obtain derivatives of the molecular diode, 2-{4-[1-cyano-2-(1-(ω-acetylsulfanylalkyl)-1H-quinolin-4-ylidene)-ethylidene]-cyclohexa-2,5-dienylidene}-malonitrile [1, CH3CO–S–CnH2n–Q3CNQ], from either 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane (TCNQF4) or 2,3,5,6-tetramethyl-7,7,8,8-tetracyano-p-quinodimethane (TMTCNQ) result in ring closure via the cyano group of the π-bridge and yield di-substituted analogues: 2-{2,3,5,6-tetrafluoro-4-[6-(10-acetylsulfanyldecyl)-3-(1-(10-acetylsulfanyldecyl)-1H-quinolin-4-ylidenemethyl)-6H-benzo[f][1,7]naphthyridin-2-ylidene]-cyclohexa-2,5-dienylidene}-malonitrile (2a) and the 2,3,5,6-tetramethyl derivative (2b). Self-assembled monolayers (SAMs) of these donor–(π-bridge)–acceptor molecular diodes exhibit asymmetric current–voltage characteristics with electron flow at forward bias from the top contact to surface C(CN)2 groups. Comparison is made with I–V curves from ultra-thin films of an organic rectifying junction in which TCNQ− is electron-donating and a donor–(σ-bridge)–acceptor diode in which TCNQ° is electron-accepting.