Structural Diversity of Octa- and Hexadecafluorinated Tin(II) and Tin(IV) Phthalocyanines

In this work crystal structures of octa- and hexadecafluoro-substituted tin(II) and tin(IV) phthalocyanines are shown. Complexes were obtained by fusing of fluorinated phthalonitriles with SnCl₂ (Method 1) and refluxing the initial reagents in 1-chloronaphthalene (Method 2). In the case of octafluorosubstituted tin complexes it has been shown that during synthesis by the Method 1, Sn(II)PcF₈ complexes are formed. At the same time, during the synthesis by the Method 2, Sn(IV)Cl₂PcF₈ complexes are obtained. It was demonstrated that not only the synthesis method but also the number of fluorine substituents affects the composition and structure of the obtained complexes. Unlike octasubstituted derivatives, only tin(IV) complexes are formed during the synthesis of hexadecafluorosubstituted phthalocyanines using both methods. Thus, when fusing tetrafluorophthalonitrile with SnCl₂, halogen atoms are exchanged and a mixture of monomeric SnF₂(PcF₁₅Cl) and dimeric Sn₂F₃(PcF₁₅Cl)₂ complexes is formed. The synthesis in solution leads to the formation of SnCl₂PcF₁₆, which crystallizes together with 1-chloronapthalene solvate molecules. The effect of heating and vacuum sublimation on the transformation of Sn(IV) phthalocyanines is also studied.