Synthesis and EPR studies of metallophthalocyanines containing four carbhexyloxybiphenyloxy substituents

Abstract

4-(4′-Carbhexyloxybiphenyloxy)phthalonitrile was synthesized by esterification of 4-(4′-carboxybiphenyloxy)phthalonitrile with hexanol in the presence of dicyclohexylcarbodiimide (DCCI). Zn(II), Co(II) and Cu(II) phthalocyanines with four carbhexyloxybiphenyloxy pendant groups on the periphery were prepared from 4-(4′-carbhexyloxybiphenyloxy)phthalonitrile and the corresponding divalent metal salts (Zn(CH 3COO) 2, CoCl 2 and CuCl 2). These new compounds have been characterized by 1H NMR, 13C NMR, FT-IR, UV–vis and mass spectroscopies. The EPR spectra obtained at room temperature indicate axially symmetric character of ligand field at the site of Co(II) and Cu(II) paramagnetic ions. Especially, the Cu(II) coordinated compounds show stronger covalency effects with neighboring N atoms with respect to Co(II) coordinated compounds. Computer programs have been written to determine Spin–Hamiltonian parameters for solid powder form of ion coordinated complexes. Orbital energy levels for magnetic electrons were determined from Spin–Hamiltonian parameters as well.