This contribution reports an integrated chemical, spectroscopic, X-ray diffractometric, and charge transport investigation of the cofacially linked metallomacrocyclic polymers [M(hp)O]n where M = Si and Ge and hp = hemiporphyrazinato. The synthesis of the new = Si compound (from Si(hp)Cl2 and Si(hp)(OH)2) and modified syntheses of the M = Ge analogue are reported. Optical spectra are discussed as a function of M and X for the various M(hp)X2 derivatives. Radiotracer studies of the degree of polymerization using M(hp)(O3H)2 precursors yield Ò values for typical [M(hp)O]n samples of 20 (M = Si) and 50 (M = Ge). On the basis of data for monomeric M(hp)X2 derivatives, both vibrational and high-resolution solid-state 13C NMR spectra of the [M(hp)O]n polymers can be assigned in terms of a cofacially linked polymer architecture. X-ray diffraction data suggest that the [M(hp)O]n polymers are crystalline and structurally similar; however, the crystal structures are not similar to that of [Fe(hp)O]n nor to those of the analogous [M(Pc)O]n polymers, Pc = phthalocyaninato. Doping of the [M(hp)O]n polymers with iodine using several procedures results in iodine uptake but no significant increase in electrical conductivity. It appears that iodination is accompanied by destruction of the polymer M-O-M framework.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry