Structure and Property Correlations in Heavy Atom Radical Conductors

摘要

The synthesis and solid-state characterization of the resonance-stabilized heterocyclic thia/ selenazyl radicals 1a-4a is described. While all the radicals crystallize in undimerized slipped π-stacked arrays, the four crystal structures do not constitute an isomorphous setrn; crystals of 1a and 3a belong to the orthorhombic space group P2_12_12_1, while those of 2a and 4a belong to the monoclinic space group P2_1. The origin of the structural dichotomy can be traced back to the packing of the radicals in the P2t structure, which maximizes intermolecular Se-Se' contacts. There are marked differences in the transport properties of the two groups. Variable temperature conductivity measurements reveal high, but activated, conductivity for the monoclinic pair (2a/4a), with σ(298 K) > 10~(-3) S cm~(-1). The application of physical pressure increases the conductivity of both compounds, with σ(298 K) at 5 GPa reaching 0.5 S cm~(-1) for 2a and 2 S cm~(-1) for . 4a. Variable-temperature magnetic susceptibility measurements indicate strong antiferromagnetic (AFM) coupling for the monoclinic pair 2a and 4a, the behavior of which has been modeled in terms of a molecular-field modified 1D Heisenberg chain of AFM coupled S =1/2 centers. Extended Huckel theory band structure calculations and density functional theory first principles methods have been used to develop a qualitative understanding of the conductive and magnetic properties of radicals of the type 1 -4 as a function of the degree and direction of slippage of the radical π-stacks.