4-(2',3',4',5',6'-Pentafluorobenzyloxy)phthalonitrile was employed with hexanethiol to prepare 4-(2',3',5',6'-tetrafluoro-4'-hexylthio-benzyloxy)phthalonitrile, by the selective displacement of the para-fluorine atom using K2CO3 in DMF. The new Zn(II), Ni(II) and Co(II) phthalocyanines with four, peripheral fluoro-hexylthiobenzyloxy groups were synthesized from 4-(2',3',5',6'-tetrafluoro-4'-hexylthio-benzyloxy)phthalonitiile and the corresponding divalent metal salt (Zn(CH3COO)(2), NiCl2 or COCl2). The blue-green phthalocyanines were soluble in common organic solvents. The structures of the target compounds were confirmed using elemental analysis, UV-vis, FT-IR, H-1 NMR, F-19 NMR and mass spectroscopic methods. (c) 2007 Elsevier Ltd. All rights reserved.