Semi-conducting mixed-valent X4TCNQI−/II− (X = H, F) charge-transfer complexes with C6H2(NH2)4
2020
We report further characterisation on the previously described [C6H2(NH2)4][TCNQ] charge-transfer (CT) complex. An in-depth analysis of the crystallographic data aided by spectroscopic methods indicates the compound is mixed-valent with TCNQI−/II− species. The analogous F4TCNQ CT complex has been synthesised and spectroscopic methods suggest that [C6H2(NH2)4][F4TCNQ] is also mixed-valent. Electrical conductivity measurements on both complexes indicate semi-conductor behaviour, with [C6H2(NH2)4][TCNQ] exhibiting a σ300K = 9.8 × 10−4 S cm−1 and an Ea = 0.10(1) eV. Density functional theory studies on both CT complexes reveal band structures suggestive of ambipolar transport, with a super-exchange mechanism.
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