skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF) and its 1:1 radical cation salts [DC-TAF][X]: Preparation and solid-state properties of BF{sub 4{minus}}, ClO{sub 4{minus}}, and FSO{sub 3{minus}} derivatives

Abstract

Reductive coupling of 4,5-dichloro-1,2,3-dithiazolylium chloride yields trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF), the first example of this heterofulvalene system. Ab initio molecular orbital (B3LYP/6-31G**) calculations on prototypal TAF confirm that the closed shell {sup 1}A{sub g} state lies 22 kcal mol{sup {minus}1} below the {sup 3}B{sub u} diradical triplet. Cyclic voltammetry on DC-TAF reveals two reversible oxidation waves at 0.80and 1.25 V (in CH{sub 3}CN, reference SCE). The EST signal (g = 2.0117) of the radical cation [DC-TAF]{sup +} (in SO{sub 2}(1)) exhibits a five=line hyperfine coupling pattern with a{sub n} = 0.096 mT. DC-TAF forms a series of 1:1 radical ion salts [DC-TAF][X] by electrooxidation in the presence of tetrahedral counterions (X{sup {minus}} = BF{sub 4}{sup {minus}}, ClO{sub 4}{sup {minus}}, FSO{sub 3}{sup {minus}}). The crystal structures of these salts are isomorphous, monoclinic space group P2{sub 1}/n. and consist of one-dimensional ladder-like arrays of [DC-TAF]{sup +} radical cations bridged by S---S contacts ranging from 3.5 to 3.7 {angstrom}. Variable-temperature conductivity and magnetic measurements on [DC-TAF][ClO{sub 4}] indicate Mott insulator behavior, with a measured band gap of 0.30 eV.

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Arkansas, Fayetteville (US)
Sponsoring Org.:
Natural Sciences and Engineering Research Council of Canada (NSERC); National Science Foundation (NSF); USDOE
OSTI Identifier:
20000099
DOE Contract Number:  
FG02-97ER45668
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 121; Journal Issue: 28; Other Information: PBD: 21 Jul 1999; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; SYNTHESIS; DESIGN; HETEROCYCLIC COMPOUNDS; RADICALS; DERIVATIZATION; TTF

Citation Formats

Barclay, T J, Beer, L, Cordes, A W, Haddon, R C, Itkis, M I, Oakley, R T, Preuss, K E, and Reed, R W. Trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF) and its 1:1 radical cation salts [DC-TAF][X]: Preparation and solid-state properties of BF{sub 4{minus}}, ClO{sub 4{minus}}, and FSO{sub 3{minus}} derivatives. United States: N. p., 1999. Web. doi:10.1021/ja990933z.
Barclay, T J, Beer, L, Cordes, A W, Haddon, R C, Itkis, M I, Oakley, R T, Preuss, K E, & Reed, R W. Trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF) and its 1:1 radical cation salts [DC-TAF][X]: Preparation and solid-state properties of BF{sub 4{minus}}, ClO{sub 4{minus}}, and FSO{sub 3{minus}} derivatives. United States. https://doi.org/10.1021/ja990933z
Barclay, T J, Beer, L, Cordes, A W, Haddon, R C, Itkis, M I, Oakley, R T, Preuss, K E, and Reed, R W. Wed . "Trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF) and its 1:1 radical cation salts [DC-TAF][X]: Preparation and solid-state properties of BF{sub 4{minus}}, ClO{sub 4{minus}}, and FSO{sub 3{minus}} derivatives". United States. https://doi.org/10.1021/ja990933z.
@article{osti_20000099,
title = {Trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF) and its 1:1 radical cation salts [DC-TAF][X]: Preparation and solid-state properties of BF{sub 4{minus}}, ClO{sub 4{minus}}, and FSO{sub 3{minus}} derivatives},
author = {Barclay, T J and Beer, L and Cordes, A W and Haddon, R C and Itkis, M I and Oakley, R T and Preuss, K E and Reed, R W},
abstractNote = {Reductive coupling of 4,5-dichloro-1,2,3-dithiazolylium chloride yields trans-4,4{prime}-dichloro-1,1{prime},2,2{prime},3,3{prime}-tetrathiadiazafulvalene (DC-TAF), the first example of this heterofulvalene system. Ab initio molecular orbital (B3LYP/6-31G**) calculations on prototypal TAF confirm that the closed shell {sup 1}A{sub g} state lies 22 kcal mol{sup {minus}1} below the {sup 3}B{sub u} diradical triplet. Cyclic voltammetry on DC-TAF reveals two reversible oxidation waves at 0.80and 1.25 V (in CH{sub 3}CN, reference SCE). The EST signal (g = 2.0117) of the radical cation [DC-TAF]{sup +} (in SO{sub 2}(1)) exhibits a five=line hyperfine coupling pattern with a{sub n} = 0.096 mT. DC-TAF forms a series of 1:1 radical ion salts [DC-TAF][X] by electrooxidation in the presence of tetrahedral counterions (X{sup {minus}} = BF{sub 4}{sup {minus}}, ClO{sub 4}{sup {minus}}, FSO{sub 3}{sup {minus}}). The crystal structures of these salts are isomorphous, monoclinic space group P2{sub 1}/n. and consist of one-dimensional ladder-like arrays of [DC-TAF]{sup +} radical cations bridged by S---S contacts ranging from 3.5 to 3.7 {angstrom}. Variable-temperature conductivity and magnetic measurements on [DC-TAF][ClO{sub 4}] indicate Mott insulator behavior, with a measured band gap of 0.30 eV.},
doi = {10.1021/ja990933z},
url = {https://www.osti.gov/biblio/20000099}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 28,
volume = 121,
place = {United States},
year = {1999},
month = {7}
}