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Inner Cavity (inner + cavity)

Distribution by Scientific Domains
Chemistry100%

Selected Abstracts

Complexation and Dynamic Switching Properties of Fluorophore-Appended Resorcin[4]arene Cavitands

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 5 2010
Laura D. Shirtcliff
Abstract Fluorophore-appended resorcin[4]arene-based cavitands having pyrene (2) and anthracene (3) moieties attached to the rims were prepared by short synthetic routes. Both undergo reversible temperature- and acid- (CF3COOD) induced vase,,,kite switching as evidenced by 1H NMR spectroscopy. The 1H NMR spectra also suggest that suitably sized solvents, such as [D8]toluene, efficiently solvate the cavity, reducing the conformational flexibility. In [D12]mesitylene, both cavitands undergo remarkably stable host-guest inclusion complexation with cycloalkanes. The larger cavity of 3 preferentially hosts cyclohexane, whereas the smaller cavity of 2 forms the most stable complex with cyclopentane. The propensity for the cavitands to facilitate ,,, stacking between the chromophores was confirmed by both 1H NMR and fluorescence spectroscopy. The interchromophoric interaction is strongly solvent-dependent: ,,, stacking between the pyrene moieties of 2 is not as efficient in [D8]toluene, as it solvates the inner cavity and prevents the two chromophores from approaching each other. Fluorescence studies revealed an unexpectedly large conformational flexibility of the cavitand structures both in the vase and kite forms, which was further confirmed by molecular dynamics simulations. Excimer formation is most preferred in [D12]mesitylene when the cavities are empty, whereas efficient solvation or guest binding in the interior spaces reduces the propensity for excimer formation. The observed high conformational flexibility of the cavitands in solution explains previous differences from the behavior of related systems in the solid state. This study shows that the rigid, perfect vase and kite geometries found for bridged resorcin[4]arene cavitands in the solid state are largely a result of crystal packing effects and that the conformational flexibility of the structures in solution is rather high. [source]

Syntheses, structures, and supramolecular properties of giant ,-expanded macrocyclic oligothiophenes

HETEROATOM CHEMISTRY, Issue 5 2007
Masahiko Iyoda
Fully conjugated ,-expanded macrocyclic oligothiophenes with 60,-, 90,-, 120,-, 150,-, and 180,-electron systems (1,5) were synthesized using modified McMurry coupling reaction as a key step. Compound 1 was converted into macrocyclic oligo(2,5-thienylene-ethynylene) 6 using bromination-dehydrobromination procedure. X-ray analysis of 1 revealed a unique molecular and packing structure, reflecting a round, planar shape with nanoscale inner cavity. Interestingly, 2 and 3 self-aggregate in the solid state to form nanowires. The structure of fibrous aggregates was established by scanning electron microscopic and atomic force microscopic analyses. Compounds 1,6 exhibit multi-step reversible redox behavior with fairly low first oxidation potentials, reflecting their cyclic conjugation. Doping of 1,3 with iodine gives semiconductors owing to their ,-donor properties and ,,, stacking ability. © 2007 Wiley Periodicals, Inc. 18:460,466, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20337 [source]

Synthesis and Preferred All- syn Conformation of C3 -Symmetrical N -(Hetero)arylmethyl Triindoles

CHEMISTRY - A EUROPEAN JOURNAL, Issue 28 2008

Abstract A new series of C3 -symmetrical N -(hetero)arylmethyl triindoles has been synthesized in a straightforward procedure. The structure and conformation in the solid state have been determined for three derivatives (3, 4, and 6) by X-ray crystallographic analysis. In all three cases, the molecules adopt a tripodal conformation with all of the flexible arms directed towards the same side, thereby delimiting an inner cavity. Compound 6 crystallizes and forms C3 -symmetric dimeric cagelike complexes. Guest molecules of chloroform and water are confined within the resulting cavities with stabilization by different intermolecular interactions; this highlights the potential of these compounds in the construction of supramolecular systems. A computational analysis has been performed to predict the most stable conformers. As a general trend, a preference for a conformation with all branches directed to the same side has been predicted. Comparison between theoretical and experimental results indicates that the computational level selected for the present study, B3LYP/6-31G*, is able to reproduce both the minimum energy conformations and the rotation barriers about the NCH2 bond. [source]

Host,Guest Interaction of Chaperonin GroEL and Water-Soluble CdTe Quantum Dots and its Size-Selective Inclusion

CHEMPHYSCHEM, Issue 15 2008
Chaoqing Dong
Abstract Some nanoparticles, such as quantum dots (QDs), are widely used in the biological and biomedical fields due to their unique optical properties. However, little is currently known about the interaction between these nanoparticles and biomolecules. Herein, we systemically investigated the interaction between chaperonin GroEL and water-soluble CdTe QDs based on fluorescence correlation spectroscopy (FCS), capillary electrophoresis, and fluorescence spectrometry. We observed that some water-soluble CdTe QDs were able to enter the inner cavity of GroEL and formed an inclusion complex after the activation of chaperonin GroEL with ATP. The inclusion of GroEL was size-selective to QDs and only small QDs were able to enter the inner cavity. The inclusion could suppress the fluorescence quenching of the QDs. Meanwhile, we evaluated the association constant between chaperonin GroEL and CdTe QDs by FCS. Our results further demonstrated that FCS was a very useful tool for study of the interaction of QDs and biomolecules. [source]