An assembled compound (BEDT-TTF)2[Mn2Cl5(EtOH)] (1) consisting of two structural lattices of Mn(II)-Cl one-dimensional (1-D) chains and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) stacking layers was synthesized by electrochemical crystallization. Compound 1 crystallized in triclinic space group P-1 (#2) with a = 13.1628(5) Å, b = 20.3985(9) Å, c = 7.4966(3) Å, α = 98.3498(8)°, β = 104.980(1)°, γ = 74.602(2)°, V = 1868.3(1) Å3, and Z = 2. The 1-D chains and the stacking layers are aligned along the c-axis of the unit cell. The 1-D chain is described as [Mn2Cl5(EtOH)]∞- in which two Mn(II) ions and four Cl- ions form a ladder-like chain with Kagomé (cuboidal) sublattices, and the remaining Cl- ion and an ethanol molecule cap the edge-positioned Mn(II) ions of the chains. The BEDT-TTF molecules are packed between the Mn-Cl chains (ac-plane), the intermolecular S⋯S contacts of which are approximately found in the range 3.440(2)-3.599(2) Å. The packing feature of BEDT-TTF molecules is very similar to that of (BEDT-TTF)2ClO4(TCE)0.5 (TCE = 1,1,2-trichloroethane) (J. Am. Chem. Soc., 105, 297 (1983)). Regarding the electronic state of each BEDT-TTF molecule, Raman spectroscopic analysis and ESR study revealed the presence of half-valence BEDT-TTF molecules (charge delocalization) in 1. Magnetic measurements clearly demonstrated that the paramagnetic spins on the 1-D chain [Mn2Cl5(EtOH)]∞- arrange antiferromagnetically in the low-temperature region. Additionally, 1 exhibits metallic conductivity in the temperature range 2.0-300 K (σ = 21 S cm-1 at 300 K and 1719 S cm-1 at 2.0 K), due to the contribution of the stacked BEDT-TTFs. Consequently, these peculiarities that correspond to antiferromagnetic/metallic conductivity demonstrate the "bi-functionality" of 1.
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Ceramics and Composites
- Condensed Matter Physics
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry