Optical and structural characteristics of PMMA films doped with a new anisometric EuIII complex

Acta Crystallogr B Struct Sci Cryst Eng Mater. 2019 Aug 1;75(Pt 4):570-577. doi: 10.1107/S205252061900578X. Epub 2019 Jun 12.

Abstract

A new film material capable of transforming UV radiation into visible light was obtained from a highly anisometric EuIII complex with organic ligands in a polymethylmethacrylate (PMMA) matrix and then structurally characterized. An important advantage of the synthesized complex is its good solubility in organic solvents such as dichloromethane, chloroform, THF, toluene, etc. The ligand environment (flexible alkyl and cyclohexyl substituents) of the EuIII complex was selected to prevent crystallization, to inhibit the formation of defects in the structure of films and to provide its uniform distribution in the polymer during polymerization. As a result we obtain an EuIII complex of the film with remarkable thermal behavior: the complex melts to isotropic liquid without decomposition, it supercools at ambient temperature and it forms a stable amorphous material at low (up to -30°C) temperatures. The films were prepared by two methods: bulk polymerization and spin coating. A comparison of the differences of luminescent and optical characteristics of micro- and nanosized PMMA films doped with the anisometric EuIII complex is given. Based on X-ray powder diffraction and small-angle scattering data, it has been supposed that the association of EuIII complex molecules occurs in the voids of the PMMA matrix and is accompanied by the formation of a nanocrystalline phase. For films obtained by spin coating, a deeper microphase separation is demonstrated than by bulk polymerization. The dimensional characteristics of the nano-associates were determined and a correlation between the method of preparation and the type of distribution of the EuIII complex in the PMMA matrix is established.

Keywords: PMMA composite films; anisometric EuIII complex; enhanced luminescence.