Structures and physical properties of magnetic organic conductors based on bent donor molecule EDT-EDSe-TTFVS

• Published in: Synthetic Metals Vol. 162; no. 21-22; pp. 1809 - 1814
• Main Authors: Sun, Jibin, Shao, Jiafeng, Jiang, Guiyang, Lu, Xiaofeng, Zhang, Shangxi, Li, Xuexiang, Wang, Baolin, Sugimoto, Toyonari, Shao, Xiangfeng
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.12.2012; Elsevier BV; Elsevier
• Subjects: Bent donor molecule; Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Conductivity of specific materials; Electronic transport in condensed matter; Exact sciences and technology; Magnetic organic conductor; Magnetic properties and materials; Organic compounds; Physics; Polymers; organic compounds (including organic semiconductors); Spin arrangements in magnetically ordered materials (including neutron and spin-polarized electron studies, synchrotron-source x-ray scattering, etc.); Structure of solids and liquids; crystallography; Structure of specific crystalline solids; π−d interaction; Bent donor molecule; Magnetic organic conductor; π−d interaction; Antiferromagnetism; π―d interaction; Band structure; Electrical conductivity; Organic conductors; Electronic structure; Semiconductivity; Charge transfer complexes; Activation energy; Exchange interactions; Crystal structure
• ISSN: 0379-6779; 1879-3290
• DOI: 10.1016/j.synthmet.2012.07.027

[Display omitted] ► New magnetic organic conductors based on bent donor molecule EDT-EDSe-TTFVS. ► Quasi one-dimensional conduction pathway. ► Semiconducting behavior with good conductivity at room temperature. ► Antiferromagnetic interaction caused by relatively strong π–d interaction. The preparation, crystal structures, and physical properties of magnetic organic conductors based on a new bent donor molecule ethylenedithio-ethylenediseleno-tetrathiafulvalene-thioquinone-1,3-dithiolemethide (EDT-EDSe-TTFVS 3) are reported. The single crystals of 32FeCl4(EtOH) and 32FeBr4 are obtained by the electrochemical oxidation of 3 in the presence of (n-Bu4N)FeX4 (X=Cl, Br) at 45°C. Semiconducting behavior is observed with moderate conductivities of 4.0 and 0.6Scm−1 for 32FeCl4(EtOH) and 32FeBr4, respectively. In the crystal structures of both salts, the donor molecules and magnetic FeX4− ions form segregated layers. Within the organic layer, the donor molecules form columnar stacks, and the intra-columnar intermolecular overlap integrals are larger than the inter-columnar ones, resulting in the quasi one-dimensional electronic structures. There are atomic close contacts between the donor and FeX4 ion layers, which gives rise to the antiferromagnetic interaction of Fe(III) d-spins in both salts. Moreover, the Fe(III) d-spins in 32FeBr4 are subject to the antiferromagnetic ordering at 5K due to the strong π–d and d–d interactions.