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

Abstract

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.

Authors:
; ; ; ;  [1]; ;  [2]
  1. Argonne National Lab., IL (USA)
  2. North Carolina State Univ., Raleigh (USA)
Publication Date:
OSTI Identifier:
6950137
DOE Contract Number:  
W-31-109-ENG-38; FG05-86ER45259
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry; (USA)
Additional Journal Information:
Journal Volume: 29:9; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; BISMUTH IODIDES; SUPERCONDUCTIVITY; ETHYLENE; TTF; CHEMICAL PREPARATION; ELECTRONIC STRUCTURE; EXPERIMENTAL DATA; ALKENES; BISMUTH COMPOUNDS; DATA; ELECTRIC CONDUCTIVITY; ELECTRICAL PROPERTIES; HALIDES; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; INFORMATION; IODIDES; IODINE COMPOUNDS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PHYSICAL PROPERTIES; SYNTHESIS; 360601* - Other Materials- Preparation & Manufacture; 360603 - Materials- Properties

Citation Formats

Geiser, U, Wang, H H, Budz, S M, Lowry, M J, Williams, J M, Ren, Jinqing, and Whangbo, Myunghwan. Polymeric anions leading to novel packing motifs in donor-radical salts: Synthesis and crystal and band electronic structure of (BEDT-TTF)BII sub 4. United States: N. p., 1990. Web. doi:10.1021/ic00334a007.
Geiser, U, Wang, H H, Budz, S M, Lowry, M J, Williams, J M, Ren, Jinqing, & Whangbo, Myunghwan. Polymeric anions leading to novel packing motifs in donor-radical salts: Synthesis and crystal and band electronic structure of (BEDT-TTF)BII sub 4. United States. doi:10.1021/ic00334a007.
Geiser, U, Wang, H H, Budz, S M, Lowry, M J, Williams, J M, Ren, Jinqing, and Whangbo, Myunghwan. Wed . "Polymeric anions leading to novel packing motifs in donor-radical salts: Synthesis and crystal and band electronic structure of (BEDT-TTF)BII sub 4". United States. doi:10.1021/ic00334a007.
@article{osti_6950137,
title = {Polymeric anions leading to novel packing motifs in donor-radical salts: Synthesis and crystal and band electronic structure of (BEDT-TTF)BII sub 4},
author = {Geiser, U and Wang, H H and Budz, S M and Lowry, M J and Williams, J M and Ren, Jinqing and Whangbo, Myunghwan},
abstractNote = {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.},
doi = {10.1021/ic00334a007},
journal = {Inorganic Chemistry; (USA)},
issn = {0020-1669},
number = ,
volume = 29:9,
place = {United States},
year = {1990},
month = {5}
}