Magnetic/Conducting Hybrid Compound Composed of 1-D Chain [MnII2Cl5(EtOH)]∞− and BEDT-TTF Stacking Layer

Abstract An assembled compound (BEDT-TTF) 2 [Mn 2 Cl 5 (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) A, b =20.3985(9) A, c =7.4966(3) A, α =98.3498(8)°, β =104.980(1)°, γ =74.602(2)°, V =1868.3(1) A 3 , 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 [Mn 2 Cl 5 (EtOH)] ∞ − in which two Mn(II) ions and four Cl − ions form a ladder-like chain with Kagome (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) A. The packing feature of BEDT-TTF molecules is very similar to that of (BEDT-TTF) 2 ClO 4 (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 [Mn 2 Cl 5 (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.