Electric and Magnetic Properties of 4, 4′, 5, 5′-Tetramethoxy-2, 2′-Dithiobiphenyl Iodide(6/7) – A New Radical Cation Salt Containing Polyiodide Chains

Intercalation and Deintercalation of Iodine into 2,3,8,9-Tetramethoxydibenzo[c,e][1,2]- dithiin: A Detailed Mechanistic Study of a Gas−Solid Reaction Leading to an Organic Conductor

“…Earlier EPR experiments revealed the charge transfer from DTB to iodine (about 0.25 electron per DTB molecule for the fully loaded compound), and Raman spectroscopy suggested the presence of either triiodide or pentaiodide . The dc conductivity along the needle b axis, i.e., parallel to the iodine chains and to the DTB stacks, is almost constant between 270 and 360 K (5 S cm -1 ; p-type conduction; Seebeck coefficient 50 mV K -1 ) …”

“…In contrast to metals, the conductivity may be anisotropic due to different charge-transfer mechanisms ), is a member of a class of stacked organic conductors, first discovered in 1954, that exhibit electrical conductivity. , It becomes p-conducting when it is doped with iodine 1 Structure of 2,3,8,9-tetramethoxydibenzo[ c,e ]- [1,2]dithiin (“dithiobiphenyl” = “DTB”), 1 1 Crystallographic Data for Pure and Iodine-Doped DTB pure DTB 7 DTB·I 1.16 6 crystal system monoclinic monoclinic space group P 2 1 / a C 2/ c a /pm 2332.9(5) 2312.3(10) b /pm 715.1(1) 698.5(2) c /pm 1313.5(3) 2555.8(10) β/deg 133.84(1) 123.52(3) V /10 6 pm 3 1580.5 3441.6 Z 4 8 ρ calc /g cm -3 1.41 2.78 …”

“…2,4 It becomes p-conducting when it is doped with iodine. 5 DTB can be cocrystallized with iodine from acetonitrile, toluene, or chloroform to give a host-guest complex with the approximate composition DTB‚I 1. 16 .…”

“…6 The dc conductivity along the needle b axis, i.e., parallel to the iodine chains and to the DTB stacks, is almost constant between 270 and 360 K (5 S cm -1 ; p-type conduction; Seebeck coefficient 50 mV K -1 ). 5 Iodine inclusion into DTB can also be accomplished by exposing DTB crystals to iodine vapor. However, nothing is known about the intermediate stages of the intercalation and deintercalation.…”