Ueber einige makromolekulare Halbleiter mit Porphyrazinstruktur

Abstract

AbstractPolymers with a structure similar to phthalocyanine were made by melting of tetracyanothiophene (I), tetracyanofuran (II), octacyano‐P.P.P‐triphenylphospholidine (III), tetramethyl‐bis(maleonitriledithiolato)cuprate (IVa), and copper bis(maleonitriledithiolato)cuprate (IVb) with copper acetylacetonate and with other metal acetylacetonates in different molar ratios and with o‐phthalodinitrile (V). The conductivities at a pressure of 1,500 kp‐cm.−2 were in the range of 5.7 × 10−5 to 10−14 ohm−1 cm.−1. The conductivities decreased with decreasing aromatic character of the starting nitriles. In some cases of polychelates with two different incorporated metals higher conductivities were found than were expected from the two unimetallated polychelates. For various metal polychelates of (I) there seems to be a relationship between the conductivities and the ionization potentials and the ionic radii of the metals. Measurements of the thermal EMF showed p‐conduction. Seebeck coefficients were independent of the temperature for the polychelates made from (I) and (II) and were dependent on the temperature for the polychelates made from (III). A certain polychelate made from (III) had a thermal EMF of 40 mv. for ΔT × 30°. Polymers with a structure similar to tetraazadiarylene‐diisoindolenine were obtained by fusing of (I) with p‐phenylenediamine, and of (I), (IVa), (IVb), and nickel bis(maleonitriledithiolato)cuprate (IVc) with 2,6‐diaminopyridine and by melting of 2,5‐diamino‐3,4‐dicyanothiophene with or without CuCl2. The structure was proved by elementary analysis and by IR spectroscopy. The conductivities were in the range of 7.1 × 10−3 to 1.0 × 10−9 ohm−1 cm.−1. The polymers made from (IVb) and (IVc) showed smaller conductivities than did those from (IVb) and (IVc).