Preparation and properties of azaTCNQ- anion salts and mixed azaTCNQ-/TCNQ- salts of N-alkylpyridinium and related cations.

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The [Cation]+ATCNQ− type salts were prepared, where ATCNQ− is (4-dicyanomethyl-1-pyridinio)dicyanomethanide anion, so-called AzaTCNQ− anion, and [Cation]+ are N-alkylpyridinium, 4-cyano-N-alkylpyridinium, (4-methyl-1-pyrazinio)dicyanomethanide, N-alkylquinolinium (alkyl=Me and Et), N-methylacridinium, and N-methylphenazinium. Electrical resistivities of these salts as compacted samples fall in the range 106–109 Ωcm at 25 °C. The mixed ATCNQ−/TCNQ\newdot salts (TCNQ\newdot=7,7,8,8-tetracyano-p-quinodimethan radical anion) of N-alkylpyridinium and -quinolinium cations also were prepared; [Cation]+ (ATCNQ−)0.1(TCNQ\newdot)0.9([Cation]+=N-methylpyridinium, N-ethylpyridinium, and N-ethylquinolinium) and [N-methylquinolinium]+(ATCNQ−)0.17(TCNQ\newdot)0.83 whose electrical resistivities (104–106 Ωcm at 25 °C) are somewhat smaller than those of the corresponding TCNQ\newdot salts. Stackings of ATCNQ− and TCNQ\newdot anions are discussed on the basis of electronic reflectance and ESR spectra. The [Cation]+ATCNQ− salts react with iodine in hexane to give [Cation]+ATCNQ−·Ix ([Cation]+=N-methyl- and N-ethylpyridinium and -quinolinium; x=3.2–3.9). They exhibit electrical resistivities of 104–106 Ωcm at 25°C, which are lower by the 102–103 order than the resistivities of the undoped [Cation]+ATCNQ− salts.
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