Synthesis, spectral, and electrochemical characterization of the first arsenic(V)-phthalocyanines.
The first arsenic(V)-phthalocyanines, [As(tbpc)X(2)](+), where tbpc denotes tetra(tert-butyl)phthalocyaninate, C(48)H(48)N(8)(2-) and X = F, Cl, and Br) have been prepared through an appropriate oxidative addition process to a highly soluble arsenic(III) derivative, [As(tbpc)](+). Among them, [As(tbpc)F(2)](+) has been isolated as PF(6)(-) salt. Unlike conventional metal derivatives of phthalocyanines, they show a significantly red-shifted (by >1000 cm(-1)) Q-band and facile reduction of the macrocyclic ligand (redox potentials for [As(tbpc)F(2)](+) have been determined by cyclic voltammetry; 1.13 V vs ferricinium(+)/ferrocene (tbpc(-/2-)), -0.45 V (tbpc(2-/3-)), and -0.90 V (tbpc(3-/4-)), of which the values are anodically shifted by about 1 V) as compared to those of conventional phthalocyanines. Although the anomaly in their spectral and electrochemical properties is similar to that of the known antimony analogues, the arsenic-phthalocyanines have been found less stable.
National Institute for Materials Science, 1-2-1, Sengen, Tsukuba, Ibaraki, 305-0047, Japan. ISAGO.Hiroaki@nims.go.jp
Hiroaki
H
Isago
Yutaka
Y
Kagaya
D000965:Antimony / Q000737:chemistry; D001151:Arsenic / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008024:Ligands; D008958:Models, Molecular; D010084:Oxidation-Reduction; D012995:Solubility; D021241:Spectrometry, Mass, Electrospray Ionization; D013055:Spectrophotometry, Infrared
D056831:Coordination Complexes; D007211:Indoles; D054833:Isoindoles; D008024:Ligands; D000965:Antimony; D001151:Arsenic; C013647:phthalocyanine