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Title: Neutron diffraction evidence for unusual cohesive H-bonding interactions in. beta. -(BEDT-TTF)/sub 2/X organic superconductors. [. beta. -bis(ethylenedithio)tetrathia fulvalene X; X = AuI/sub 2/ or I/sub 3/]

Abstract

In order to determine the nature and exact geometries of the interionic interactions that are responsible for crystal cohesion between the sheetlike networks of radical cation molecules and the halide-containing anions in the layered organic conductors of the type ..beta..-(ET)/sub 2/X, the authors have undertaken low-temperature (20 K) neutron diffraction studies of the X/sup -/ = AuI/sub 2//sup -/ and I/sub 3//sup -/ salts. For these synthetic organic superconductors, ..beta..-(ET)/sub 2/AuI/sub 2/ has the highest T/sub c/ (approx. 5K) at ambient pressure, and ..beta..-(ET)/sub 2/I/sub 3/ has the highest T/sub c/ (approx. 8 K) under a nonhydrostatic pressure of 1.3 kbar. The discovery of very short H...I contacts in ..beta..-(ET)/sub 2/AuI/sub 2/ is surprising because such interactions are generally assumed to be weak. There are important implications for the design and synthesis of new ..beta..-(ET)/sub 2/X systems where the X/sub n//sup -/ anions contain halide (I, Br, Cl, F) atoms, namely, that H-bonding interactions of the type H...X play a major role in determining the crystal cohesive forces between donors and anions thereby controlling compound formation.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab., IL
OSTI Identifier:
5534174
DOE Contract Number:  
W-31-109-ENG-38; AC02-76CH00016
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.; (United States)
Additional Journal Information:
Journal Volume: 108:13
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; GOLD IODIDES; INTERMOLECULAR FORCES; SUPERCONDUCTIVITY; IODIDES; TTF; EXPERIMENTAL DATA; NEUTRON DIFFRACTION; SUPERCONDUCTORS; COHERENT SCATTERING; DATA; DIFFRACTION; ELECTRIC CONDUCTIVITY; ELECTRICAL PROPERTIES; GOLD COMPOUNDS; HALIDES; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; INFORMATION; IODINE COMPOUNDS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC SULFUR COMPOUNDS; PHYSICAL PROPERTIES; SCATTERING; TRANSITION ELEMENT COMPOUNDS; 360603* - Materials- Properties; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Emge, T J, Wang, H H, Geiser, U, Beno, M A, Webb, K S, and Williams, J M. Neutron diffraction evidence for unusual cohesive H-bonding interactions in. beta. -(BEDT-TTF)/sub 2/X organic superconductors. [. beta. -bis(ethylenedithio)tetrathia fulvalene X; X = AuI/sub 2/ or I/sub 3/]. United States: N. p., 1986. Web. doi:10.1021/ja00273a061.
Emge, T J, Wang, H H, Geiser, U, Beno, M A, Webb, K S, & Williams, J M. Neutron diffraction evidence for unusual cohesive H-bonding interactions in. beta. -(BEDT-TTF)/sub 2/X organic superconductors. [. beta. -bis(ethylenedithio)tetrathia fulvalene X; X = AuI/sub 2/ or I/sub 3/]. United States. https://doi.org/10.1021/ja00273a061
Emge, T J, Wang, H H, Geiser, U, Beno, M A, Webb, K S, and Williams, J M. Wed . "Neutron diffraction evidence for unusual cohesive H-bonding interactions in. beta. -(BEDT-TTF)/sub 2/X organic superconductors. [. beta. -bis(ethylenedithio)tetrathia fulvalene X; X = AuI/sub 2/ or I/sub 3/]". United States. https://doi.org/10.1021/ja00273a061.
@article{osti_5534174,
title = {Neutron diffraction evidence for unusual cohesive H-bonding interactions in. beta. -(BEDT-TTF)/sub 2/X organic superconductors. [. beta. -bis(ethylenedithio)tetrathia fulvalene X; X = AuI/sub 2/ or I/sub 3/]},
author = {Emge, T J and Wang, H H and Geiser, U and Beno, M A and Webb, K S and Williams, J M},
abstractNote = {In order to determine the nature and exact geometries of the interionic interactions that are responsible for crystal cohesion between the sheetlike networks of radical cation molecules and the halide-containing anions in the layered organic conductors of the type ..beta..-(ET)/sub 2/X, the authors have undertaken low-temperature (20 K) neutron diffraction studies of the X/sup -/ = AuI/sub 2//sup -/ and I/sub 3//sup -/ salts. For these synthetic organic superconductors, ..beta..-(ET)/sub 2/AuI/sub 2/ has the highest T/sub c/ (approx. 5K) at ambient pressure, and ..beta..-(ET)/sub 2/I/sub 3/ has the highest T/sub c/ (approx. 8 K) under a nonhydrostatic pressure of 1.3 kbar. The discovery of very short H...I contacts in ..beta..-(ET)/sub 2/AuI/sub 2/ is surprising because such interactions are generally assumed to be weak. There are important implications for the design and synthesis of new ..beta..-(ET)/sub 2/X systems where the X/sub n//sup -/ anions contain halide (I, Br, Cl, F) atoms, namely, that H-bonding interactions of the type H...X play a major role in determining the crystal cohesive forces between donors and anions thereby controlling compound formation.},
doi = {10.1021/ja00273a061},
url = {https://www.osti.gov/biblio/5534174}, journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 108:13,
place = {United States},
year = {1986},
month = {6}
}