Effect of non-peripheral fluorosubstitution on the structure of metal phthalocyanines and their films

• Published in: Dyes and pigments Vol. 192; p. 109442
• Main Authors: Sukhikh, Aleksandr, Bonegardt, Dmitry, Klyamer, Darya, Basova, Tamara
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 01-08-2021
• Subjects: Fluorine substituents; Metal phthalocyanines; Single crystal structure; Thin films; X-ray diffraction; Thin films; X-ray diffraction; Fluorine substituents; Metal phthalocyanines; Single crystal structure
• ISSN: 0143-7208; 1873-3743
• DOI: 10.1016/j.dyepig.2021.109442

In this work, we study crystal structures and thin films of tetrasubstituted metal phthalocyanines with fluorine substituents in non-peripheral positions, MPcF4-np (M = Cu(II), Co(II), Pd(II), Fe(II), Pb(II), VO). The effect of fluorosubstitution in non-peripheral positions of the phthalocyanine macrocycle on the structure of single crystals and thin films, and intermolecular interactions is elucidated and compared with that of other fluorinated phthalocyanine derivatives. MPcF4-np (M = Cu(II), Pd(II), Fe(II)) are isostructural and crystallize in the monoclinic P21/c space group, while CoPcF4-np forms two polymorphs (P21 and P21/c). Monoclinic PbPcF4-np (P21/n) is packed in chains along the c axis, in which one PbPcF4-np molecule is oriented “up” and two neighboring molecules face “down”. Two triclinic (P-1) phases were obtained for VOPcF4-np. For the better visualization and comparison of intermolecular contacts in different MPcF4-np, the analysis of Hirshfeld surfaces (HS) was carried out. All investigated MPcF4-np derivatives form thin films with a strong preferred orientation. The effect of the positions of F-substituents on the electronic absorption spectra of MPcF4 solutions and thin films is also discussed.
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•Structure of non-peripheral fluorosubstituted phthalocyanines were studied.•Effect of the position of F-substituents on intermolecular interactions was elucidated.•Position of F-substituents causes changes in the structure and spectra of thin films.