Optical investigations of the metal-insulator transition in a low-dimensional organic conductor (EDT-TTF)4[Hg3I8]

The polarized reflectance spectra of single crystals of the low-dimensional organic conductor (EDT-TTF)₄[Hg₃I₈] undergoing a metal-insulator phase transition at a temperature T < 35 K have been presented. The spectral region of the study is 700–6000 cm^?1 (0.087–0.74 eV), and the temperature range is 300–9 K. It has been shown that the reflectance spectra are determined by a system of quasi-free electrons of the upper half-occupied molecular π-orbitals, which form a half-filled metallic band in the crystals. A high anisotropy of the spectra and their temperature dependences have been found. For two polarizations, the quantitative analysis of the spectra at 100 and 25 K has been performed in the framework of the phenomenological Drude model, the effective mass and the width of the initial metallic π-electron band have been deter-mined, and it has been found that the conducting system in the crystals has a quasi-one-dimensional character. As temperature decreases, the spectra demonstrate substantial changes indicating the formation of the energy gap (or pseudogap) in the spectrum of electronic states in the range of ～1500–2500 cm^?1. In the low-frequency region (700–1600 cm^?1), a vibrational structure has been observed, and the most intense feature of the structure (ω = 1340 cm^?1) is caused by the interaction of electrons with intramolecular vibrations of the C=C bonds of the EDT-TTF molecule. For temperatures of 15 and 9 K, the analysis of the spectra has been performed in the framework of the theoretical “phase phonon” model taking into account the interaction of electrons with the intramolecular vibrations. It has been concluded that the metal-insulator transition observed in the reflectance spectra of the crystals is similar to the Peierls dielectric transition that occurs in a system of electrons coupled with the intramolecular vibrations of the molecules forming the crystal.     

Magnetic Coupling and Optical Properties of the S6‐Dodecakis(trifluoromethyl)fullerene Radical Anions in the Layered Salt (PPN+)[C60(CF3)12.−]

Poly(trifluoromethyl)fullerene S₆‐C₆₀(CF₃)₁₂ was reduced by sodium fluorenone ketyl in the presence of (PPN)Cl (PPN=bis(triphenylphosphine)iminium) to afford the salt (PPN)[C₆₀(CF₃)₁₂] ( 1 ), which contains C₆₀(CF₃)₁₂^.? radical anions. In the crystal structure of 1 , C₆₀(CF₃)₁₂^.? layers alternate with the PPN⁺ cations. There are short F ??? F contacts between C₆₀(CF₃)₁₂^.? radical anions within the layers but no C ??? C contacts. DFT calculations revealed that the negative charge on C₆₀(CF₃)₁₂^.? is distributed mainly between sp² carbon and fluorine atoms, whereas spin density is localized mainly on the fullerene‐cage sp² carbon atoms. IR and UV/Vis/NIR spectra in the solid state and solution showed characteristic changes relative to those of neutral S₆‐C₆₀(CF₃)₁₂ due to the formation of radical anions. The solid‐state electronic spectrum of 1 exhibits a single broad band at 738 nm attributed to C₆₀(CF₃)₁₂^.?. Crystals of 1 show a narrow EPR signal with g=2.0025 (ΔH=0.45 mT) at 300 K. The temperature dependence of the integral intensity follows the Curie–Weiss law with a negative Weiss temperature of ?11.8 K (30–300 K) indicating antiferromagnetic interaction of spins. This dependence was approximated by the Heisenberg model for one‐dimensional chains of antiferromagnetically interacting spins with exchange interaction J/k_B=?9.1 K. It was assumed that magnetic interaction between the C₆₀(CF₃)₁₂^.? spins in the layers is mediated by short F ??? F contacts.