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61.
Harald Müller Anna Puig Molina B. Zh. Narymbetov L. V. Zorina S. S. Khasanov R. P. Shibaeva 《无机化学与普通化学杂志》1998,624(9):1492-1496
The title compounds were prepared from 1,3,4,6-tetrathiapentalene-2,5-dione ( 1 ) in one step via the in situ generated intermediate 2-oxo-1,3-dithiole-4,5-dithiolate (dmid; 2 ). The X-ray single crystal structure of (Et4N)2[Zn(dmid)2] ( 3 a ) gave the tetragonal space group P43212 with a = b = 13.810(2) Å, c = 16.480(3) Å, and Z = 4. (n-Bu4N)2[Zn(dmid)2] ( 3 b ) gave the triclinic space group P 1 with a = 11.947(4) Å, b = 14.665(5) Å, c = 16.662(8) Å, α = 100.21(3)°, β = 104.46(3)°, γ = 110.73(3)°, and Z = 2. 相似文献
62.
L. V. Zorina S. S. Khasanov B. Zh. Narymbetov R. P. Shibaeva A. I. Kotov É. B. Yagubskii 《Crystallography Reports》2001,46(2):219-224
A new radical cation salt based on bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with the tetrahedral anion GaCl 4 ? , namely, (BEDT-TTF)4(GaCl4)2 · C6H5CH3, has been synthesized. The crystal structure of this salt is determined by X-ray diffraction analysis [a = 31.757(2) Å, b = 6.8063(3) Å, c = 34.879(2) Å, β = 90.453(4)°, V = 7538.8(7) Å3, space group I2/c, and Z = 4]. In the structure, the radical cation layers alternate with the anion layers along the c-axis. The anion layers consist of the GaCl 4 ? tetrahedra and solvent molecules. The packing of BEDT-TTF molecules in the radical cation layer differs from that in the structure of the known salt (BEDT-TTF)2GaCl4, even though both compounds exhibit semiconductor properties. 相似文献
63.
Lemouchi C Vogelsberg CS Zorina L Simonov S Batail P Brown S Garcia-Garibay MA 《Journal of the American Chemical Society》2011,133(16):6371-6379
As a point of entry to investigate the potential of halogen-bonding interactions in the construction of functional materials and crystalline molecular machines, samples of 1,4-bis(iodoethynyl)bicyclo[2.2.2]octane (BIBCO) were synthesized and crystallized. Knowing that halogen-bonding interactions are common between electron-rich acetylenic carbons and electron-deficient iodines, it was expected that the BIBCO rotors would be an ideal platform to investigate the formation of a crystalline array of molecular rotors. Variable temperature single crystal X-ray crystallography established the presence of a halogen-bonded network, characterized by lamellarly ordered layers of crystallographically unique BIBCO rotors, which undergo a reversible monoclinic-to-triclinic phase transition at 110 K. In order to elucidate the rotational frequencies and the activation parameters of the BIBCO molecular rotors, variable-temperature (1)H wide-line and (13)C cross-polarization/magic-angle spinning solid-state NMR experiments were performed at temperatures between 27 and 290 K. Analysis of the (1)H spin-lattice relaxation and second moment as a function of temperature revealed two dynamic processes simultaneously present over the entire temperature range studied, with temperature-dependent rotational rates of k(rot) = 5.21 × 10(10) s(-1)·exp(-1.48 kcal·mol(-1)/RT) and k(rot) = 8.00 × 10(10) s(-1)·exp(-2.75 kcal·mol(-1)/RT). Impressively, these correspond to room temperature rotational rates of 4.3 and 0.8 GHz, respectively. Notably, the high-temperature plastic crystalline phase I of bicyclo[2.2.2]octane has a reported activation energy of 1.84 kcal·mol(-1) for rotation about the 1,4 axis, which is 24% larger than E(a) = 1.48 kcal·mol(-1) for the same rotational motion of the fastest BIBCO rotor; yet, the BIBCO rotor has three fewer degrees of translational freedom and two fewer degrees of rotational freedom! Even more so, these rates represent some of the fastest engineered molecular machines, to date. The results of this study highlight the potential of halogen bonding as a valuable construction tool for the design and the synthesis of amphidynamic artificial molecular machines and suggest the potential of modulating properties that depend on the dielectric behavior of crystalline media. 相似文献
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