New phthalocyanines bearing tetra(hydroxyethylthio) functionalities

New phthalocyanines containing bulky electron rich substituents

“…lithium was used to obtain the metal-free derivative 2, while the metal salt [Zn(OAc) 2 , CoCl 2 ] and a suitable solvent, such as pyridine were required for the metal phthalocyanines 3 and 4. This procedure yields a mixture of four geometric isomers with a thioethanol group at the 2-or 3-position of each benzo-ring in the phthalocyanine molecule [22]. These phthalocyanines are soluble to a certain extent in donor solvents such as DMSO, DMF and pyridine.…”

“…For the preparation of phthalocyanines carrying thioethanol moieties fi rstly the cyano compound, 4-(2-hydroxyethylthio)phthalonitrile has been synthesized through base-catalyzed aromatic nitro displacement of 4-nitro phthalonitrile with 2-hydroxyethylmercaptane in DMSO; Na 2 CO 3 was used as the base for this nucleophilic aromatic displacement [22]. This reaction has been used in the preparation of a variety of ether or thioethersubstituted phthalonitriles [23][24][25].…”

“…4-nitrophthalonitrile was prepared according to a reported procedure [41]. 4-(2-hydroxyethylthio)-phthalonitrile (1) and tetra(2-hydroxyethylthio)phthalocyanine (2), tetra(2-hydroxyethylthio)zinc(II)phthalocyanine (3) and tetra(2-hydroxyethyl thio)cobalt(II)-phthalocyanine (4) was prepared according to a reported procedure [22,28]. Tetrakis(9-anthroylethylthio)phthalocyanine (5).…”

Synthesis and characterization of new monomeric and polymeric phthalocyanines

“…There was a single Q band (Q band transition) for 5, whereas a split Q band, as expected, and two strong bands were in the visible region for 6 and 7. 15 The split Q band, which is characteristic for metal-free phthalocyanines, was observed at k max values of 709 and 678 and 704 and 676 nm with shoulders at 650 and 644 nm for 6 and 7, respectively, which indicated the monomeric species; the monomeric species with D 2h symmetry showed two intense absorptions around 700 nm. 15,16 On the other hand, such split-Q band absorptions are due to the p!p* transition of this fully conjugated 18p electron systems.…”

“…15 The split Q band, which is characteristic for metal-free phthalocyanines, was observed at k max values of 709 and 678 and 704 and 676 nm with shoulders at 650 and 644 nm for 6 and 7, respectively, which indicated the monomeric species; the monomeric species with D 2h symmetry showed two intense absorptions around 700 nm. 15,16 On the other hand, such split-Q band absorptions are due to the p!p* transition of this fully conjugated 18p electron systems. 17 In the case of an H 2 SO 4 solution of 7, the primary band in the visible region was broadened and shifted to a longer wavelength (72 nm).…”