Synthetic conducting materials XII. TCNQ and polyiodide charge transfer salts with hexaazacyclotetradecine nickel complex donor

Abstract

A hexa-aza-macrocyclic nickel(II) complex, Ni(HAPP), of large conjugated pi-system is readily obtained from template condesation of 2,9-diamino-1,10-phenanthroline with 2,9-dichloro-1,10-phenanthroline in the presence of the nickel(II) ion. Both of the charge transfer salts of Ni(HAPP) with TCNQ and polyiodide have been prepared and characterized by elemental analysis, infrared, electronic, and mass spectroscopy. The polyiodide existed in I5− form characterized by Raman spectroscopy. There are two steps decomposition of the I5− ion to eliminate I2, I5−—I3−—I−, when analyzed by thermal gravimetry. The differential thermal analytical results evidented that very weak interaction between Ni(HAPP) and I5− occured. the variable temperature magnetic susceptibility and electron paramagnetic resonance spectroscopy were employed to investigate the behavior of the unpaired electrons in the solid state crystal. An interesting detail of the magnetic susceptibility will be presented and discussed. The EPR spectra of these compoinds show a novel type of conjugated system, related to some extent to porphin and phthalocyanin. The ESCA spectra and electric conductivity have been measured and will be discussed.