TY - JOUR
T1 - Inclusion Complexes Oriented in Thermotropic Liquid-Crystalline Solvents Studied with Carbon-13 NMR
AU - Marjanska, Malgorzata
AU - Goodson, Boyd M.
AU - Castiglione, Franca
AU - Pines, Alexander
PY - 2003/11/20
Y1 - 2003/11/20
N2 - The inclusion complex of cryptophane-A and chloroform dissolved in two nonchiral liquid-crystalline environments was investigated via 13C NMR. Stable solutions of oriented complexes were prepared using aromatic (ZLI 1132) and aliphatic (ZLI 1695) thermotropic nematic liquid crystals as solvents; ordering of the complexes was manifested by the 1H- 13C dipolar splitting of the 13C resonance of labeled chloroform. In both solutions, the dipolar splitting for the bound ligands was substantially larger than that obtained for the free ligands, indicating a significant increase in ligand ordering upon complexation despite the absence of direct contact with the oriented solvent molecules. A similar enhancement in ordering was observed for complexed ligands compared to that for free ligands in both liquid-crystalline solvents. Also, the application of heteronuclear decoupling to the ZLI 1695 solution resulted in a reduced line width for the bound 13C chloroform resonance, suggesting that a significant component of the observed line broadening may originate from intermolecular couplings between host and guest molecules. These results demonstrate the potential for using restored dipolar couplings to investigate structural and dynamical aspects of inclusion complexes in solution.
AB - The inclusion complex of cryptophane-A and chloroform dissolved in two nonchiral liquid-crystalline environments was investigated via 13C NMR. Stable solutions of oriented complexes were prepared using aromatic (ZLI 1132) and aliphatic (ZLI 1695) thermotropic nematic liquid crystals as solvents; ordering of the complexes was manifested by the 1H- 13C dipolar splitting of the 13C resonance of labeled chloroform. In both solutions, the dipolar splitting for the bound ligands was substantially larger than that obtained for the free ligands, indicating a significant increase in ligand ordering upon complexation despite the absence of direct contact with the oriented solvent molecules. A similar enhancement in ordering was observed for complexed ligands compared to that for free ligands in both liquid-crystalline solvents. Also, the application of heteronuclear decoupling to the ZLI 1695 solution resulted in a reduced line width for the bound 13C chloroform resonance, suggesting that a significant component of the observed line broadening may originate from intermolecular couplings between host and guest molecules. These results demonstrate the potential for using restored dipolar couplings to investigate structural and dynamical aspects of inclusion complexes in solution.
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U2 - 10.1021/jp030431e
DO - 10.1021/jp030431e
M3 - Article
AN - SCOPUS:0344100075
SN - 1520-6106
VL - 107
SP - 12558
EP - 12561
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 46
ER -