Experimental and Theoretical Studies of the Optical Properties of the Schiff Bases and Their Materials Obtained from o-Phenylenediamine.

Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde , respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of and were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk -butyl groups in . The luminescence of and in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of was observed (λ = 350 nm). For , this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λ = 350 nm) for and , respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for /Si and /Si samples, respectively. Furthermore, the materials of the /Si and /Si exhibited broad emission. This feature can allow for using these compounds in LED diodes.