Crystal structure and metallization mechanism of the π-radical metal TED.

ABSTRACT: Radical electrons tend to localize on individual molecules, resulting in an insulating (Mott-Hubbard) bandgap in the solid state. Herein, we report the crystal structure and intrinsic electronic properties of the first single crystal of a π-radical metal, tetrathiafulvalene-extended dicarboxylate (TED). The electrical conductivity is up to 30 000 S cm^-1 at 2 K and 2300 S cm^-1 at room temperature. Temperature dependence of resistivity obeys a T ³ power-law above T > 100 K, indicating a new type of metal. X-ray crystallographic analysis clarifies the planar TED molecule, with a symmetric intramolecular hydrogen bond, is stacked along longitudinal (the a-axis) and transverse (the b-axis) directions. The π-orbitals are distributed to avoid strong local interactions. First-principles electronic calculations reveal the origin of the metallization giving rise to a wide bandwidth exceeding 1 eV near the Fermi level. TED demonstrates the effect of two-dimensional stacking of π-orbitals on electron delocalization, where a high carrier mobility of 31.6 cm² V^-1 s^-1 (113 K) is achieved.

SUBMITTER: Kobayashi Y 

PROVIDER: S-EPMC8162741 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature