Macrocyclic Phenanthrolinediamides: Synthesis, Structure and Quantum Chemical Modeling of Anion Binding

Based on acyldichloride of 1,10-phenanthroline-2,9-dicarboxilic acid and alkylenediamines a set of new macrocyclic 1,10-phenanthroline-2,9-dicarboxamides has been prepared. The size of macrocyclic cavity in these compounds ranges from 14 to 24 atoms. The structure of 24-membered macrocycle consists of two phenanthroline moieties which are linked together by two alkylenediamine spacers. The structure of all the obtained compounds was confirmed by a combination of spectral analysis methods, including NMR, IR spectroscopy, and mass spectrometry. The structure of two macrocycles was unambiguously confirmed by single-crystal X-ray diffraction analysis. Using the quantum chemical calculations, we studied the potential ability of the obtained macrocycles to effectively bind anions of various nature and geometry. The computations were carried out both in the gas phase approximation and considering the specific solvation for the F-and HF2-anions. The calculations indicate that the macrocycle 5 is capable of acting as a receptor for F-and HF2-anions in both organic and aqueous media.