Studies on the Interaction of Poly(phenylene methylene) with Silver(I) and Hexacarbonylchromium(0)

Complexes of poly(phenylene methylene) (PPM) with silver(I) ions and tricarbonylchromium(0) moieties, respectively, were synthesized. ¹³C NMR spectra indicate interaction of phenylene groups with silver(I) and chromium(0), and peak broadening implies dynamic behavior of the silver(I) complexes, with all phenylene groups temporarily involved in coordination, in contrast to the chromium complexes. About 5-10% of the phenylene groups are coordinated to metal atoms. ¹H NMR and IR spectra, in the case of chromium(0), and the solubility of silver salts in the presence of PPM provide further evidence of coordination. The complexes are soluble in chloroform, but the silver complexes decay in tetrahydrofuran (second-order kinetics were observed in an example). The photoluminescence (fluorescence) of PPM is maintained upon complexation, although coordination of silver(I) seems to favor the so-called blue phase of PPM relative to the green phase by a factor of approximately two in PL spectra. The pronounced absorption of the tricarbonylchromium(0) units interferes with the blue phase, which almost disappears at a concentration of 50 mg/mL in PLE spectra, whereas the emission maximum of the green phase is hardly affected. This leads to a confinement of the emitted wavelength range of PPM. Thus, the perceived optical emission of PPM can be modified by coordinated entities.