The compounds I (Z)-2-(phenyl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile with one side (2,4,5-MeO-), one symmetrical (2Z,2'Z)-2,2'-(1,4-phenylene)bis(3-(2,4,5-trimethoxyphenyl)acrylonitrile), II (both sides with (2,4,5-MeO-), and three positional isomers with pyridine (Z)-2-(pyridin-2- 3, or 4-yl)-3-(2,4,5-trimethoxyphenyl)acrylonitrile, III-V were synthetized and characterized by UV-Vis, fluorescence, IR, H1-NMR, and EI mass spectrometry as well as single crystal X-ray diffraction (SCXRD). The optical properties were strongly influenced by the solvent (hyperchromic and hypochromic shift), which were compared with the solid state. According to the solvatochromism theory, the excited-state (μe) and ground-state (μg) dipole moments were calculated based on the variation of Stokes shift with the solvent's relative permittivity, refractive index, and polarity parameters. SCXRD analyses revealed that the compounds I and II crystallized in the monoclinic system with the space group, P21/n and P21/c, respectively, and with Z = 4 and 2. III, IV, and V crystallized in space groups: orthorhombic, Pbca; triclinic, P-1; and monoclinic, P21 with Z = 1, 2, and 2, respectively. The intermolecular interactions for compounds I-V were investigated using the CCDC Mercury software and their energies were quantified using PIXEL. The density of states (DOS), molecular electrostatic potential surfaces (MEPS), and natural bond orbitals (NBO) of the compounds were determined to evaluate the photophysical properties.
Keywords: DFT studies; MEPS; NBO; PIXEL; acrylonitrile derivatives; optical properties; solution and solid state.