Halbleiter-Komposite aus [(Me₃Sn)₃Fe_xCo_1-x(CN)₆]-Aggregaten (0 < x ≤ 1) und Polypyrrol / Semiconducting Composites Involving [(Me₃Sn)₃Fe_xCo_1-x(CN)₆]-Assemblies and Polypyrrole

Abstract

Pyrrole has been incorporated into the channel-like cavities of polymers of the type: [(Me3Sn)3FeIIIxCoIII1-x(CN)6] with 0 < x ≤ 1. The resulting black composites involving polypyrrole (Ppy) and Fe(II) display electrical conductivities σ between ca. 10-5 and 10-1 S · cm-1. Usually, composites prepared in the presence of small amounts of H2O exceed those in conductivity resulting under strictly anhydrous conditions owing to notably lower thermal activation energies (0.04 to 0.08 eV). An oxidative polymerization mechanism differing from that assumed for “classical” modes of Ppy generation is likely, since the N(pyrrole)/Fe(II) ratio turns always out to be ≥ 1. Exposure of a composite with x = 1 to an atmosphere of NH3 causes a decrease of σ from 1.5 · .10-1 to 2.7 · .10-6 S · cm-1; this NH3 uptake, and the concomitant change of σ, appear to be partially reversible. 1-Methylpyrrole, 2,5-dimethylpyrrole and aniline are oxidized by, and incorporated into, the organotin polymer, too, but the resulting σ-values do not exceed ∼10-9 S · cm-1.

Unprecedented N-E Bond Cleavage (E=Sn, Pb) by R4N+ Ions (R=nBu, nPr): Formation, Architecture, and Multinuclear Magnetic Resonance Spectroscopy of Novel Supramolecular [(R4N)(Me3E)2M(CN)6⋅H2O] Assemblies (M=Fe, Co)

“…MS measurements were made on a Varian 331 A mass spectrometer and electrical conductivity measurements were conducted as described in ref. [5]. X-ray powder diffractograms were obtained on a Philips PW 1050 instrument (Cu Ka source and Ni filter), while the single-crystal X-ray study was performed on a Syntex P2 1 four-circle diffractometer.…”

“…[4] Similar observations have been made on the exposure of 1 a and 1 c to pyrrole. [5] In an atmosphere of aniline, yellow 2 a converted into a dark green solid which contained both Fe II and Fe III . [4] Although 2 a ± 2 d, unlike 1 a and 1 b, should contain both bridging (to E atoms) and nonbridging (i.e.…”