关键词:
MOLECULAR rotation
ROTORS -- Dynamics
STATORS
ROTATIONAL motion
SOLID state electronics
X-ray diffraction
ACTIVATION (Chemistry)
TEMPERATURE effect
摘要:
Samples of 4,4'-bis(3,3,3-tri-d(5)-phenylpropynyl)biphenyl 2, 9,10-bis(3,3,3-tri-d(5)-phenylpropynyl)anthracene 3, 1,4-bis(3,3,3-tri-d(5)-phenylpropynyl)naphthalene 4, and 4,4'-bis(3,3,3-tri-d(5)-phenylpropynyl)-1, 1'-bi naphthyl 5 were prepared via a Sonogashira coupling of 3,3,3-tri-d(5)-phenylpropyne 7 and the appropriate aryl dibromide. Single crystal X-ray diffraction structures were obtained for an o-xylene clathrate of 2 and for solvent-free crystals of 3. All four molecular rotors were characterized by CPMAS C-13 NMR experiments with varying contact times in order to determine whether the carbon signals of the central rotator group could be selectively enhanced and studied without interference or overlap of signals from the deuterated stator, which is insensitive to the {H-1}-C-13 cross-polarization method. It was shown that the C-13 signals of the natural abundance rotator group can be selectively observed with short contact times (ca. 50 mu s) without interference from other C-13 signals in the molecule. Variable-temperature CPMAS C-13 NMR studies with a crystalline o-xylene solvate of biphenylene rotor 2 suggested a 2-fold flipping process in the fast exchange regime, even at temperatures as low as 199 K (-74 degrees C). Indirect support for this was obtained by studies carried out with a disordered, solvent-free solid, obtained by fast precipitation from hexanes and dichloromethane, which displayed slower dynamics within the same temperature range with an activation energy of 8.7 kcal/mol and a pre-exponential factor of 4.9 x 10(9) s(-1). Confirmation of an exchange process in the megahertz regime for the crystalline solvate was obtained by variable-temperature quadrupolar echo H-2 NMR data acquired with samples prepared with a deuterated biphenylene rotator and a natural abundance stator. Although rotational exchange occurs in the solvated samples with a slightly lower barrier of 7.4 kcal/mol, the main difference with the precipitated solid comes from t