Upon reduction of a 1H‐cyclobuta[de]naphthalene‐4,5‐diylbis(diarylmethylium) species, a new CC bond is formed between the Cα and Cortho atoms of the two chromophores, which presents an unprecedented coupling pattern for the dimerization of two trityl units. By attaching an annulated cyclobutane ring at the opposite peri position of the naphthalene core, the distance between the Cα carbon atoms was elongated beyond the limit of σ‐bond formation through “scissor effects”. The suppression of CαCα bond formation, which would lead to hexaphenylethane‐type compounds, is key to the first successful isolation of the α,o‐adducts. The 5‐diarylmethylene‐6‐triarylmethyl‐1,3‐cyclohexadiene unit in the α,o‐adducts is stable, and isomerization of the cyclohexadiene unit into an aromatic system was not observed. The newly formed CαCortho bond was cleaved upon two‐electron oxidation to regenerate the dicationic dye.

Nanoparticles of two molecule-based conductors namely, TTFTCNQ and TTF[Ni(dmit) 2 ] 2 , have been prepared in organic solution in the presence of ionic or non-ionic species bearing a long-chain alkyl group, acting as growth controlling agents. The size, morphology and state of dispersion of the nanoparticles depended on the nature of the growth-controlling agent and the reaction temperature. In the presence of a long-chain-alkyl-based ionic liquid at -50 °C, electron micrographs evidence that TTFTCNQ nano-objects are frequently elongated, whereas TTF[Ni(dmit) 2 ] 2 nanoparticles are aggregated. In the presence of a neutral long-chain-alkyl-based imine at room temperature, nanoparticles are spherical (mean diameter less than 20 nm) and well dispersed. Vibration spectra evidence that the amounts of charge transfer for TTFTCNQ and TTF[Ni(dmit) 2 ] 2 as nano-objects are very similar to those for the same phases as bulk materials. According to the thermoanalytical investigations, the prepared nanoparticles are stable thermally up to approximately 200 °C, their decomposition is generally a multi-step process. Their heat treatment results in various sulfur containing volatiles (CS 2 , SO 2 , H 2 S), moreover HCN is also detected in the case of nitrogen containing molecules (TCNQ).

ARTICLE INFO ABSTRACTKeywor ds: Nanopartlcles Tetrathiafulvalene salts Mlxed-valence conductors Electrocristallization technique Growth-controillng agentThe work described in this paper is directed towards the electrosynthesis of TTFClo, 77 as spherical nanoparticles by using amphiphilic molecules, behaving as growth