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

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) ?, b=20.3985(9) ?, c=7.4966(3) ?, ALPHA=98.3498(8)°, BETA=104.980(1)°, GAMMA= 74.602(2)°, V=1868.3(1) ?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 [Mn2Cl5(EtOH)]INFINITY- 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) ?. 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)]INFINITY- arrange antiferromagnetically in the low-temperature region. Additionally, 1 exhibits metallic conductivity in the temperature range 2.0-300 K (SIGMA=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.