Lyapunov A. Fluorenonocrownophanes and catenanes on their base: synthesis, structure and properties

Object of investigation: Crownophanes and catenanes containing fragment of 2,7-dioxyfluorenone. Aim of investigation: Elaboration of method of synthesis of a new class of the crownophanes – fluorenonocrownophanes and catenanes on their base; studying of structure and properties of obtained compounds. Methods of investigation and equipment: organic synthesis, IR, UV, NMR spectroscopy, mass spectrometry, X-ray crystal structure analysis, methods of computer aided molecular modeling. Theoretical results and their novelty: Crownophanes including 2,7-dioxyfluorenone fragment as macrocyclic element have been synthesized for the first time. In solution, according to NMR 1Н spectroscopy and molecular modeling data, fluorenonocrownophanes mainly possess conformations with the closed intramolecular cavity which are stabilized by intramolecular interactions of aromatic fragments of a molecule. A variety of spectral methods including mass spectrometry, UV and NMR spectroscopy used to study of interactions betweenthe crownophanes and paraquat. A linear correlation was found between a free energy of complexation and position of the charge-transfer band associated with the complex formation. It was found that fluorenonocrownophanes are perspective molecular matrixes for catenanes synthesis. On an example fluorenonocrownophane containing fluorenone and naphthalene fragments connected triethylene glycol units, an opportunity of existence of the catenane in the one “frozen” translation isomer at ambient temperature for the first time has been shown. Practical results and their novelty: The methods of synthesis of a new class of the crownophanes – fluorenonocrownophanes which are perspective ligands for electron deficient substrates like paraquat have been elaborated. The dependences which were found between induced chemical shifts of protons of paraquat and crownophanes in NMR 1H spectra their mixtures and between charge-transfer band position and stability constants of corresponding complexes let us easy to evaluate complexes stability with different substrates without routine measurements. It is shown, that the most stable complexes with paraquat are formed by crownophanes containing tetraethylene glycol units and not dependent of second aromatic fragment. The methods of synthesis have been elaborated and for the first time synthesized [2]catenanes which cyclic components are fluorenonocrownophanes and cyclobis(paraquat-p-phenylene). Subject and the degree of introduction: Publications, reports at the scientific conferences, using the results of work in the scientific and pedagogical practice of establishments of higher education and Scientific Research Institutes of Ukraine. Efficiency of introduction is provided by elaboration of methods of synthesis of a new class of the crownophanes – fluorenonocrownophanes and [2]catenanes on their base. Sphere of use: Chemistry.