TY - JOUR
T1 - Recent Synthetic Advances of Tetrathiafulvalene-Based Organic Conductors
AU - Otsubo, Tetsuo
AU - Takimiya, Kazuo
PY - 2004
Y1 - 2004
N2 - The synthetic chemistry of tetrathiafulvalene (TTF)-type electron donors has been markedly promoted by introducing two key reactions, the one-pot preparation of 1,3-dichalcogenole-2-chalcogenones from terminal alkynes and the formation of heterocyclic rings via transalkylation on a chalcogen atom. In combination with a conventional trialkyl phosphite-promoted coupling reaction of 1,3-dichalcogenole-2-chalcogenones, the first reaction constitutes a ready access to the tetrachalcogenafulvalene skeleton. As a result, a number of previously inaccessible TTF-type electron donors were readily obtained. These included tetraselenafulvalene (TSF) derivatives, the selenium/sulfur or selenium/tellurium hybrid systems, dimeric TSFs linked with a single spacer group, and sophisticated stacked TSF phanes. The second reaction is very useful in constructing additional heterocyclic ring(s) on the tetrachalcogenafulvalene skeleton. A wide variety of five-, six-, and seven-membered heterocycle-fused TTF-type compounds were thus synthesized. These were systematically examined for superior electron donors of conductive molecular complexes. This study resulted in the discovery of two novel electron donors, methylenedithio-tetraselenafulvalene and methylenedithio-diselenadithiafulvalene, that form unique superconductors with exceptionally high conductivities at room temperature. The scopes and limitations of these synthetic reactions are described in connection with the recent research trends of TTF-based organic (super)conductors.
AB - The synthetic chemistry of tetrathiafulvalene (TTF)-type electron donors has been markedly promoted by introducing two key reactions, the one-pot preparation of 1,3-dichalcogenole-2-chalcogenones from terminal alkynes and the formation of heterocyclic rings via transalkylation on a chalcogen atom. In combination with a conventional trialkyl phosphite-promoted coupling reaction of 1,3-dichalcogenole-2-chalcogenones, the first reaction constitutes a ready access to the tetrachalcogenafulvalene skeleton. As a result, a number of previously inaccessible TTF-type electron donors were readily obtained. These included tetraselenafulvalene (TSF) derivatives, the selenium/sulfur or selenium/tellurium hybrid systems, dimeric TSFs linked with a single spacer group, and sophisticated stacked TSF phanes. The second reaction is very useful in constructing additional heterocyclic ring(s) on the tetrachalcogenafulvalene skeleton. A wide variety of five-, six-, and seven-membered heterocycle-fused TTF-type compounds were thus synthesized. These were systematically examined for superior electron donors of conductive molecular complexes. This study resulted in the discovery of two novel electron donors, methylenedithio-tetraselenafulvalene and methylenedithio-diselenadithiafulvalene, that form unique superconductors with exceptionally high conductivities at room temperature. The scopes and limitations of these synthetic reactions are described in connection with the recent research trends of TTF-based organic (super)conductors.
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U2 - 10.1246/bcsj.77.43
DO - 10.1246/bcsj.77.43
M3 - Article
AN - SCOPUS:0842284130
VL - 77
SP - 43
EP - 58
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 1
ER -