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Synthesis, Crystal Structure, and Characterization of the Charge‐Transfer Salt (BEDT‐TTF)[Fe(C 2 O 4 )Cl 2 ](CH 2 Cl 2 ), {BEDT‐TTF = Bis(ethylenedithio)tetrathiafulvalene}
Author(s) -
Zhang Bin,
Zhang Yan,
Gao Zengqiang,
Chang Guangcai,
Su Shaokui,
Wang Dongwei,
Guo Yanjun,
Zhu Daoben
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402112
Subject(s) - chemistry , tetrathiafulvalene , crystallography , triclinic crystal system , crystal structure , raman spectroscopy , molecule , dimer , formal charge , stereochemistry , physics , organic chemistry , optics
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(C 2 O 4 )Cl 2 – ] n , and the solvent CH 2 Cl 2 , are described and interpreted. Electrochemical oxidation of neutral BEDT‐TTF in the presence of [(C 2 H 5 ) 3 NH][Fe(C 2 O 4 )Cl 2 ] in a CH 2 Cl 2 /CH 3 OH solution yields crystals of 1 , which crystallizes in triclinic form. In 1 , 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 CH 2 Cl 2 molecules. The donor layers are separated by sheets of [Fe(C 2 O 4 )Cl 2 – ] 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 σ rt = 1.8 × 10 –5 S/cm.