Excited states of selected hydrazo-compounds on the example of 5-nitro-2-(2-phenylhydrazinyl)pyridine and its 3-, 4- or 6-methyl isomers

Abstract

Syntheses of 5-nitro-2-(2-phenylhydrazinyl)pyridine (5-nitro-2-phenylhydrazopyridine), 3-methyl-5-nitro-2-(2-phenylhydrazinyl)pyridine (3-methyl-5-nitro-2-phenylhydrazopyridine), 4-methyl-5-nitro-2-(2-phenylhydrazinyl)pyridine (4-methyl-5-nitro-2-phenylhydrazopyridine) and 6-methyl-5-nitro-2-(2-phenylhydrazinyl)pyridine (6-methyl-5-nitro-2-phenylhydrazo-pyridine) have been described. Electronic absorption and emission spectra of the compounds in the solid state and in various solvents have been measured at room temperature and discussed in terms of DFT quantum chemical calculations. The molecular structures and energy sequences of the singlet and triplet states have been determined in the B3LYP/6-311G(2d,2p) approximations. The Mulliken analysis and non-bonding orbital approach have been used in characterization of the studied compounds. It has been shown that the HOMO-LUMO transition of the studied compounds is observed in the range 23,900 ÷ 29,300 cm−1 and in this excitation the π-electrons of phenyl ring are transferred to nitro group of pyridine ring. In such a transition the hydrazo-bridge should take part as a mediator. The luminescence of the studied hydrazo-compounds is weak, not measureable in the solid state but measureable in solution.