Anion effect on crystal structure of Zn-complexes of spironaphthopyran and their chromogenic properties in solution

Effect of the anion nature on crystal structure of Zn-complexes of spironaphthopyran and their chromogenic properties in solution were studied. Complexes with zinc chloride and zinc picrate exhibited tertahedral and octahedral coordination environment of the metal ion respectively. The structure of the complex with zinc picrate demonstrates a rare example of the co-crystallization of two types of complexes differing in the number of coordinated picrate anions. The composition, stability, and absorption properties of zinc complexes in acetone essentially depend on the counter anion nature. When the coordinating ability of the counter ion increases in the range BF4- , ClO4- , NO3-, Pic-, I-, Cl-, CH3COO-, (CH3)3CCOO- the complex stability is reduced from logK = 8.7 to 2.96. This is accompanied by the chromogenic effect which is related to the decrease in the spectral shift of the long-wavelength absorption band of the complex relative to the merocyanine ligand from 846 up to 168 cm-1. The complex photo-initiated processes include fluorescence and thermally reversible dissociation. Fluorescence is characterized by band maxima in the 622-637 nm region and normal Stokes shifts of 1087-1454 cm-1 with an efficiency being weakly dependent on the anion nature. In contrast, the negative photochromism of the complexes demonstrates a significant dependence of the photo-bleaching efficiency on the anion nature in the range 0.012-0.17. The presence of a chromogenic photochromic effect along with fluorescence makes it possible to consider the complex as fluorescent switch.