Nanoscale molecular rotors that can be driven in the solid state have been realized in Cs2([18]crown-6)3[Ni(dmit)2]2 crystals. To provide interactions between the molecular motion of the rotor and the electronic system, [Ni(dmit)2]- ions, which bear one S=1/2 spin on each molecule, were introduced into the crystal. Rotation of the [18]crown-6 molecules within a Cs2([18]crown-6)3 supramolecule above 220 K was confirmed using X-ray diffraction, NMR, and specific heat measurements. Strong correlations were observed between the magnetic behavior of the [Ni(dmit)2]- ions and molecular rotation. Furthermore, braking of the molecular rotation within the crystal was achieved by the application of hydrostatic pressure.
One-dimensional dielectric (N.H.N)( infinity ) hydrogen-bonding chains of monoprotonated 1,4-diazabicyclo[2.2.2]octane (HDABCO(+)) were introduced into an electrically conducting 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) salt as the countercation structure. Room-temperature electrical conductivity was approximately 10(-)(3) S cm(-)(1), with a semiconductive behavior. The temperature-dependent dielectric constants of (HDABCO(+))(2)(TCNQ)(3) indicated a dielectric transition at 306 K. A large deuterium isotope effect for the dielectric transition (DeltaT = 70 K) was observed for the deuterated salt, (DDABCO(+))(2)(TCNQ)(3). Thermally activated order/disorder of the protons or deuteriums within the one-dimensional hydrogen-bonding chains of (HDABCO(+))( infinity ) and (DDABCO(+))( infinity ) affected the dielectric responses in the TCNQ-based semiconductors.
Molecular ''nanowire'' structures composed of the charge transfer complex of a bis-tetrathiafulvalene substituted macrocycle and tetrafluorotetracyanoquinodimethane were constructed on mica substrates by employing the Langmuir-Blodgett technique. The nanowires transferred from a dilute aqueous potassium chloride subphase had typical dimensions of 2.5 nm ؋ 50 nm ؋ 1 m. The nanowires are oriented to specific directions, corresponding to the directions of the potassium-ion array on the mica surface having sixfold symmetry. Such correlation between the nanowires and the substrate surface was also observed when a dilute aqueous rubidium chloride subphase was used. On the other hand, the correlation completely disappeared when the subphase contained divalent cations, indicating that the molecular nanowires orient by recognizing the monocation array on the mica surface. The nanowires formed by the vertical dipping method coexist with the monolayers. Only nanowire structures are, however, observed when we apply the horizontal lifting method. Based on the crystal structure of a related complex, a possible structure of the nanowires is presented. The conductivity of the nanowires was estimated to be of the order of 10 ؊3 S⅐cm ؊1 . The nanowires formed specific (regular) structures such as T-shape junctions, suggesting their use in construction of future molecular nanoscale devices.
Introduction of an ethylenedithio group into an amphiphilic bis(tetrathiafulvalene) annulated macrocycle results in the formation of organogels which produce nanodot‐array structures in Langmuir–Blodgett films (see picture). Chemical oxidation of the sulphur‐containing π‐electron system afforded size‐controllable electrically conducting nanodot structures.
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