Synthesis, structure, and physical properties of a new phenalenyl-based neutral radical crystal: Correlation between structure and transport properties in carbon-based molecular conductors

摘要

A new class of phenalenyl-based neutral radical molecular conductors has recently been reported; a distinctive feature of these molecular solids is the absence of the well-defined conducting pathway(s) that are characteristic of the organic charge-transfer salts. These radicals do not stack in the solid state, and the requisite carbon-carbon contacts are all larger than the sum of the van der Waals distances. Magnetic susceptibility measurements show that these compounds usually exist as isolated free radicals with one spin per molecule (at least over some temperature range), apparently supporting the idea that there is little interaction between the molecules in the solid state. Nevertheless, these radicals show the highest conductivity (sigma(RT) = 0.05 S/cm) of any neutral organic solid and the conduction mechanism is at present unresolved. In this article we report a structurally related radical with a resistivity five orders of magnitude higher than that of the previously reported radicals. We analyze the crystallographic and electronic structure of this solid in detail and point out some of the challenges that remain in relating structure, magnetism, and conductivity in this new class of organic solids. (C) 2003 Wiley Periodicals, Inc. [References: 14]