Polymeric anions leading to novel packing motifs in donor-radical salts: Synthesis and crystal and band electronic structure of (BEDT-TTF)BII sub 4

Journal Article · Wed May 02 04:00:00 EDT 1990 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00334a007· OSTI ID:6950137

Geiser, U; Wang, H H; Budz, S M; Lowry, M J; Williams, J M ^[1]; Ren, Jinqing; Whangbo, Myunghwan ^[2]

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1. Argonne National Lab., IL (USA)
2. North Carolina State Univ., Raleigh (USA)

In an attempt to synthesize a 2:1 salt of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF or ET, C{sub 10}H{sub 8}S{sub 8}) with soft C-H{hor ellipsis} anion contacts, which promote an increase in the superconducting transition temperature, T{sub c}, in {beta}-(ET){sub 2}X salts, the authors carried out slow electrocrystallization of ET with BiI{sub 3} and ((n-C{sub 4}H{sub 9}){sub 4}N)I in 1,1,2-trichloroethane. This led to an unexpected 1:1 salt, (ET)BiI{sub 4}, which was characterized by X-ray single-crystal diffraction. The polymeric anion, a (BiI{sub 4}{sup {minus}}){infinity} chain, contains (BiI{sub 6}) octahedra sharing edges, such that the two terminal iodide ligands are in a cis configuration. ET{sup +} cations form a network of (ET{sup +}){sub 2} dimers, connected by S{hor ellipsis}S contacts shorter than the sum of the van der Waals radii (3.6 {angstrom}). The spin susceptibility as a function of temperature, derived from ESR measurements, follows Curie's law down to 20 K, but a spin count indicates that the ESR signal is due to an impurity (less than 1%). Band electronic structure calculations on the (ET{sup +}){sub 2} layer predict (ET)BiI{sub 4} to be a semiconductor with a band gap of order 0.4 eV. Crystal data for the complex are reported. 25 refs., 4 figs., 3 tabs.

• DOE Contract Number: W-31109-ENG-38; FG05-86ER45259
• OSTI ID: 6950137
• Journal Information: Inorganic Chemistry; (USA), Journal Name: Inorganic Chemistry; (USA) Vol. 29:9; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
360601* -- Other Materials-- Preparation & Manufacture
360603 -- Materials-- Properties
ALKENES
BISMUTH COMPOUNDS
BISMUTH IODIDES
CHEMICAL PREPARATION
DATA
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
ELECTRONIC STRUCTURE
ETHYLENE
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
IODIDES
IODINE COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHYSICAL PROPERTIES
SUPERCONDUCTIVITY
SYNTHESIS
TTF