4 research outputs found
Synthesis and Electrochemical and Spectroscopic Characterization of 4,7-diamino- 1,10-phenanthrolines and Their Precursors
New approaches to the synthesis of 4,7-dichloro-1,10-phenanthrolines and their
corresponding 9H-carbazol-9-yl-, 10H-phenothiazin-10-yl- and pyrrolidin-1-yl derivatives were
developed. Their properties have been characterized by a combination of several techniques: MS,
HRMS, GC-MS, electronic absorption spectroscopy and multinuclear NMR in both solution and
solid state including 15N CP/MAS NMR. The structures of 5-fluoro-2,9-dimethyl-4,7-di(pyrrolidin-
1-yl)-1,10-phenanthroline (5d), 4,7-di(9H-carbazol-9-yl)-9-oxo-9,10-dihydro-1,10-phenanthroline-5-
carbonitrile (6a) and 4,7-di(10H-phenothiazin-10-yl)-1,10-phenanthroline-5-carbonitrile (6b) were
determined by single-crystal X-ray diffraction measurements. The nucleophilic substitutions of
hydrogen followed by oxidation produced compounds 6a and 6b. The electrochemical properties
of selected 1,10-phenanthrolines were investigated using cyclic voltammetry and compared with
commercially available reference 1,10-phenanthrolin-5-amine (5l). The spatial distribution of
frontier molecular orbitals of the selected compounds has been calculated by density functional
theory (DFT). It was shown that potentials of reduction and oxidation were in consistence with the
level of HOMO and LUMO energies