Premium
Molecular Conductors Based on peri ‐Ditellurium‐Bridged Donors,2,3‐DMTTeA and TMTTeN
Author(s) -
Fujiwara Emiko,
Fujiwara Hideki,
Narymbetov Bakhyt Zh.,
Kobayashi Hayao,
Nakata Masahiro,
Torii Hajime,
Kobayashi Akiko,
Takimiya Kazuo,
Otsubo Tetsuo,
Ogura Fumio
Publication year - 2005
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.200500167
Subject(s) - chemistry , crystallography , paramagnetism , intermolecular force , molecule , crystal (programming language) , salt (chemistry) , crystal structure , crystal engineering , metal , pauli exclusion principle , supramolecular chemistry , condensed matter physics , organic chemistry , physics , computer science , programming language
Molecular conductors based on peri ‐ditellurium‐bridged polyacene donor molecules 3,4‐dimethylanthra[1,9‐ cd :4,10‐ c ' d ']bis[1,2]ditellurole (2,3‐DMTTeA) and 2,3,6,7‐tetramethylnaphtho[1,8‐ cd :4,5‐ c ' d ']bis[1,2]ditellurole (TMTTeN) were prepared. The crystal structure analyses of neutral 2,3‐DMTTeA molecule and its cation radical salts revealed that these crystals involve an orientational disorder of the asymmetrical molecule, 2,3‐DMTTeA, and that the intermolecular network through tellurium atoms is very strong and dominant in terms of the construction of the crystal frameworks. In the crystal of (TMTTeN) 2 M(CN) 2 (M = Ag and Au), the crystal structure analyses and the extended Hückel tight‐binding band calculations indicated that these salts are quasi three‐dimensional conductors. These salts are highly conductive (720–760 S cm –1 ) and maintain metallic states down to about 50 K. Furthermore, the Ag(CN) 2 – salt exhibited a Pauli paramagnetic behavior down to 2 K [ χ (para) ≈ 2.0–2.5 × 10 –4 emu mol –1 ]. In the crystal of (TMTTeN)(SCN) 0.88 , the donor molecules are stacked to form one‐dimensional columns and construct a three‐dimensional network between the columns through the intermolecular Te ··· Te contacts. The SCN – salt is also highly conductive (590 S cm –1 ) and maintains a metallic behavior down to 4.2 K. Almost temperature‐independent paramagnetic susceptibility of (TMTTeN)(SCN) 0.88 indicates Pauli paramagnetism of this salt[ χ (para) ≈ 1.6–1.9 × 10 –4 emu mol –1 ]. A tight‐binding band structure calculation indicates that the Fermi surface of the SCN – salt is open along the b * and c * directions, but the intermolecular interactions between the donor columns are not so weak because of the three‐dimensional networkmediated by the protruded tellurium atoms. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)