New dinuclear zinc(ii) complexes with Schiff bases obtained from o-phenylenediamine and their application as fluorescent materials in spin coating deposition

Abstract

Two Zn(ii) complexes, K1 and K2, obtained from the template reaction of zinc(ii) acetate dihydrate with o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde (K1) or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde (K2), respectively, were characterized by X-ray crystallography, spectroscopic (UV-vis, fluorescence and IR), and thermal methods. In the complex [Zn₂(MeO)_1.4(OH)_0.6(L1)]·2H₂O K1, there are two binding sites in the macrocyclic ligand and they are occupied by zinc(ii) cations found in slightly distorted square pyramidal environment. The zinc(ii) cations are connected by slightly asymmetric oxo bridges with a Zn1-O14-Zn1[-x, -y + 1, -z + 1] angle of 104.8(2)°. In the dimer [Zn₂(CH₃COO)₂(L2)]·2EtOH K2, there are two crystallographically independent binding sites both occupied by zinc(ii) cations. There is a significant difference between both complexes, since in K1 only one site is independent and the second is occupied due to the application of symmetry rules, and the geometry of both sites is identical. Thin layers of the obtained Zn(ii) complexes were deposited on Si(111) by the spin coating method and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), fluorescence spectroscopy and ellipsometry. In the non-absorbing range, the value of the refractive index exhibits normal dispersion between 1.8 and 2.1 for K1_1-K1_3; and between 2.3 and 2.6 for the K2 series of samples established for long wavelengths (longer than 500 nm). The Zn(ii) complexes and their thin layers exhibited fluorescence between 534-573 nm and 495-572 nm for the compounds and the layers, respectively. The highest quantum yield of fluorescence was achieved for K2 in benzene and in the solid state ϕ = 0.78 and 0.58, respectively. The influence of the solvent polarity on the fluorescence properties of the obtained complexes was studied. Additionally, DFT calculations were performed to explain the structures and electronic spectral properties of the complexes.