Synthesis, Crystal Structure, and Characterization of the Charge‐Transfer Salt (BEDT‐TTF)[Fe(C2O4)Cl2](CH2Cl2), {BEDT‐TTF = Bis(ethylenedithio)tetrathiafulvalene}. Issue 24 (20th May 2014)

• Record Type: Journal Article
• Authors: Zhang, Bin; Zhang, Yan; Gao, Zengqiang; Chang, Guangcai; Su, Shaokui; Wang, Dongwei; Guo, Yanjun; Zhu, Daoben
• Other Names: Ouahab Lahcène sponsoringEditor.; Mori Takehiko sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 24(2014)
• Page Start: 4028
• Page End: 4032
• Publication Date: 2014-05-20
• Subjects: Organic‐inorganic hybrid composites -- Crystal engineering -- Semiconductors -- Stacking interactions -- Iron -- Charge transfer; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201402112
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The synthesis, crystal structure, Raman spectra, conductivity, and magnetism of the title charge‐transfer salt (1 ) composed of BEDT‐TTF [bis(ethylenedithio)tetrathiafulvalene], one‐dimensional [Fe(C2 O4 )Cl2 – ] n, and the solvent CH2 Cl2, are described and interpreted. Electrochemical oxidation of neutral BEDT‐TTF in the presence of [(C2 H5 )3 NH][Fe(C2 O4 )Cl2 ] in a CH2 Cl2 /CH3 OH solution yields crystals of1, which crystallizes in triclinic form. In1, two donor molecules stack in a face‐to‐face manner as a BEDT‐TTF dimer. The BEDT‐TTF dimers form a (4, 4) grid in the ab plane. The cavity of the (4, 4) grid is occupied by two CH2 Cl2 molecules. The donor layers are separated by sheets of [Fe(C2 O4 )Cl2 – ] n anions with a zigzag chain along the a axis. There are S··· S interactions between the donors, and S··· Cl interactions between the donor and the anion. On the χ vs. T plot, a broad maximum is observed around 45 K, showing the existence of antiferromagnetic interactions between the metal atoms in the low‐dimensional system. The formal charge of the donor molecules is assigned 1.0+ based on the bond lengths of the TTF core and on the Raman spectra. The material is a semiconductor with σrt = 1.8 × 10 –5 S/cm. Abstract : The title compound has been synthesized and studied, and it was found that the donor layers in the organic–inorganic hybrid charge‐transfer salt, which is composed of BEDT‐TTF 1.0+ dimers and CH2 Cl2, are separated by zigzaged anion chains. The compound is a semiconductor and shows strong antiferromagnetic interactions between the oxalate‐bridged metal atoms.