Antiferromagnetic Ordering in the Single-Component Molecular Conductor [Pd(tmdt)2]

Crystals of [Pd­(tmdt)2] (tmdt = trimethylenetetrathiafulvalenedithiolate) were prepared in order to investigate their physical properties. The electrical resistivity of [Pd­(tmdt)2] was measured on single crystals using two-probe methods and showed that the room-temperature conductivity was 100 S·cm–1. The resistivity behaviors implied that [Pd­(tmdt)2] was a semimetal at approximately room temperature and became narrow-gap semiconducting as the temperature was decreased to the lowest temperature. X-ray structural studies on small single crystals of [Pd­(tmdt)2] at temperatures of 20–300 K performed using synchrotron radiation at SPring-8 showed no distinct structural change over this temperature region. However, small anomalies were observed at approximately 100 K. Electron spin resonance (ESR) spectra were measured over the temperature range of 2.7–301 K. The ESR intensity increased as the temperature decreased to 100 K and then decreased linearly as the temperature was further decreased to 50 K, where an abrupt decrease in the intensity was observed. To investigate the magnetic state, 1H nuclear magnetic resonance (NMR) measurements were performed in the temperature range of 2.5–271 K, revealing broadening below 100 K. The NMR relaxation rate gradually increased below 100 K and formed a broad peak at approximately 50 K, followed by a gradual decrease down to the lowest temperature. These results suggest that most of the sample undergoes the antiferromagnetic transition at approximately 50 K with the magnetic ordering temperatures distributed over a wide range up to 100 K. These electric and magnetic properties of [Pd­(tmdt)2] are quite different from those of the single-component molecular (semi)­metals [Ni­(tmdt)2] and [Pt­(tmdt)2], which retain their stable metallic states down to extremely low temperatures. The experimental results and the band structure calculations at the density functional theory level showed that [Pd­(tmdt)2] may be an antiferromagnetic Mott insulator with a strong electron correlation.