Two Types of Complexes of o-Phenylenediamine with Tetracyanoquinodimethane

概要

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o-Phenylenediamine and tetracyano-p-quinodimethane (TCNQ) were shown to form two types of solid complexes with compositions of 1 : 1 and 2 : 1. The 2 : 1 complex is essentially of ionic type, while the 1 : 1 complex is characterized as of non-bonding type from the analysis of its infrared absorption spectrum. It was shown that the difference in type is reflected on the magnetic and electrical properties of these complexes. The ESR absorption or the spin concentration of the 1 : 1 complex changed irreversibly with grinding or heat-treatment (70°C), while no appreciable change was observed in the 2 : 1 complex with these treatments. The electrical resistivity is lower for the 1 : 1 complex than the 2 : 1 complex by a factor of 102. From these observations, it is considered that the ground state electronic structure of the 1 : 1 complex is in a similar situation to those of diaminopyrene-chloranil and benzidine-TCNQ complexes.
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