Synthesis, inclusion capabilities, and electrical properties of some asymmetrical cyclophanes

For the first time, we announce the synthesis of cyclo(bis-paraquat-p-phenylene-p-phenylene-carbonyl)tetrakis(hexafluorophosphate), named 'CETOBOX'. This compound exists in three tautomeric forms. These forms were evidenced by NMR data (H-1 NMR, TOCSY, COSY, and NOESY), UV-vis spectra coupled with pH measurements, and by synthesis. As the 'CETOBOX' gives 'in situ' only the corresponding monoylide, the synthesis of a new fluorescent indolizine cyclophane has been performed by a 3+2 cycloaddition. This cycloadduct, in an amidation reaction with 6-amino-beta-cyclodextrin, furnishes the final two-cavity sensor with good yields. All structures of the new compounds presented herein have been established by NMR spectroscopy. Also, theoretical methods (MM3, AM1, AM1 (COSMO), and B88LYPDFT) have been used to determine the most stable conformer structures. For the fluorescent indolizine cycloadduct, we evaluated its inclusion capabilities and for the two-cavity sensor, we measured some of its electrical properties that make it suitable for use in VOCs detection and energy conversion. (C) 2007 Elsevier Ltd. All rights reserved.