Three new polyfluorinated (E)-4-(4-bromostyryl)benzonitriles were obtained by the Horner–Wadsworth–Emmons approach to investigate intermolecular interactions in the crystalline state and the formation of co-crystals. Electrostatic surface potentials and dipole moments were calculated by ab initio methods. Three types of main intermolecular interactions were addressed to be used as a driving force to form polar co-crystals: CN⋯Br interactions lead to chain formation. Stacking of F-aromatic and H-aromatic rings is present. C–F⋯H and C–F⋯F interactions were identified, which are weak driving forces to align molecules sidewise. Crystal structures of the three stilbenes are centric. By formation of solid solutions [(E)-4-(4-bromostyryl)-2,3,5,6-tetrafluorobenzonitrile]_x·[(E)-4-(4-bromo-2,3,5,6-tetrafluorostyryl)benzonitrile]_1−x, polar properties were observed. In the case of (E)-4-(4-bromostyryl)benzonitrile·(E)-4-(4-bromo-2,3,5,6-tetrafluorostyryl)-2,3,5,6-tetrafluorobenzonitrile, a non-polar 1 ∶ 1 ordered structure is formed.

The enantiomerically pure chiral tris-chelating ligand (+)-(7S,10R)-L (L) comprising three 4,5-pinenobipyridine subunits connected through a mesityl spacer has been synthesized. Complexes of L with Ru^II and Fe^II have been prepared and characterised. NMR spectroscopy indicates that only one diastereoisomer is formed, and the CD spectra show that the complexes have the Λ configuration on the metal centre. The X-ray crystal structure of the iron complex shows that in the octahedral complex, the ligand L coils around the metal and confirms the absolute configuration. The Ru^II and Fe^II compounds were also characterised by mass spectrometry, electronic absorption, and, in the case of Ru(II), fluorescence spectroscopy. The photostability of the ruthenium compound was checked by photochemical experiments.