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Title: A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer.

Abstract

Anionic coordination polymers of divalent first-row transition elements are promising components of multifunctional molecular materials in which electronic conduction and magnetism can coexist. We report that a tetraphenylphosphonium salt containing a copper(II) dicyanamide anion has a novel pseudo-two-dimensional anionic structure and may provide a suitable electrolyte for the electrocrystallization of charge transfer salts. This (PPh{sub 4}){sub 3}Cu{sub 4}(dca){sub 11} salt crystallizes in the monoclinic space group P2{sub 1} with lattice parameters, a = 7.1911(4) {angstrom}, = 55.050(3) {angstrom}, c = 11.7964(7) {angstrom}, {beta} = 99.166(3){sup o} and V = 4610.2(7) {angstrom}{sup 3} at T = 298 K.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
940702
Report Number(s):
ANL/MSD/JA-57833
Journal ID: ISSN 1631-0748; TRN: US200824%%178
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: C. R. Chimie; Journal Volume: 10; Journal Issue: 1-2 ; 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; ANIONS; ELECTROLYTES; LATTICE PARAMETERS; MAGNETISM; POLYMERS; COPPER COMPOUNDS; CYANIDES; CRYSTALLIZATION

Citation Formats

Schlueter, J. A., Manson, J. L., Geiser, U., Materials Science Division, and Eastern Washington Univ. A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer.. United States: N. p., 2007. Web. doi:10.1016/j.crci.2006.06.011.
Schlueter, J. A., Manson, J. L., Geiser, U., Materials Science Division, & Eastern Washington Univ. A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer.. United States. doi:10.1016/j.crci.2006.06.011.
Schlueter, J. A., Manson, J. L., Geiser, U., Materials Science Division, and Eastern Washington Univ. Mon . "A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer.". United States. doi:10.1016/j.crci.2006.06.011.
@article{osti_940702,
title = {A novel pseudo-2D structural motif in an anionic copper(II) dicyanamide coordination polymer.},
author = {Schlueter, J. A. and Manson, J. L. and Geiser, U. and Materials Science Division and Eastern Washington Univ.},
abstractNote = {Anionic coordination polymers of divalent first-row transition elements are promising components of multifunctional molecular materials in which electronic conduction and magnetism can coexist. We report that a tetraphenylphosphonium salt containing a copper(II) dicyanamide anion has a novel pseudo-two-dimensional anionic structure and may provide a suitable electrolyte for the electrocrystallization of charge transfer salts. This (PPh{sub 4}){sub 3}Cu{sub 4}(dca){sub 11} salt crystallizes in the monoclinic space group P2{sub 1} with lattice parameters, a = 7.1911(4) {angstrom}, = 55.050(3) {angstrom}, c = 11.7964(7) {angstrom}, {beta} = 99.166(3){sup o} and V = 4610.2(7) {angstrom}{sup 3} at T = 298 K.},
doi = {10.1016/j.crci.2006.06.011},
journal = {C. R. Chimie},
number = 1-2 ; 2007,
volume = 10,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • The synthesis of the monoclinic polymorph of {l_brace}Cu[Hg(SCN){sub 4}]{r_brace}{sub n} is reported. The compound, as determined by X-ray diffraction of a twinned crystal, consists of mercury and copper atoms linked by {mu}{sub 1,3}-SCN bridges. The crystal packing shows a highly porous infinite 3D structure. Diagnostic resonances for the SCN{sup -} ligand and metal-ligand bonds in the IR, far-IR and Raman spectra are assigned and discussed. The electronic band structure along with density of states (DOS) calculated by the DFT method indicates that the compound is an indirect band gap semiconductor. The DFT calculations show that the observed luminescence of themore » compound arises mainly from an excited LLCT state with small MLCT contributions (from the copper to unoccupied {pi}{sup *} orbital of the thiocyanate groups). The X-band EPR spectrum of the powdered sample at room temperature reveals an axial signal with anisotropic g factors consistent with the unpaired electron of Cu(II) ion in the d{sub x}{sup 2}{sub -y}{sup 2} orbital. -- Graphical abstract: Synthesis and X-ray structure determination of the monoclinic {l_brace}Cu[Hg(SCN){sub 4}]{r_brace}{sub n} is reported. The IR, far-IR, Raman, photoluminescence as well as EPR spectra of the compound is discussed. Also, the emission and semiconducting behavior of the compound is illustrated through the density functional theory calculation of electronic band structure along with density of states. Display Omitted Research highlights: > The monoclinic {l_brace}Cu[Hg(SCN){sub 4}]{r_brace}{sub n} has been prepared. > The structure of the compound is determined by XRD of a twinned crystal. > The IR, far-IR, Raman, EPR and emission spectra of the compound is investigated. > As shown by DFT calculations, the emission bands of the compound are mainly LLCT. > Small MLCT from the copper to the thiocyanate groups contributes to these bands.« less
  • The DNA-binding domain of the GAL4 transcription factor, consisting of the 62 N-terminal amino acid residues and denoted GAL4(62*), contains a novel Zn(II){sub 2}Cys{sub 6} or Cd(II){sub 2}Cys{sub 6} binuclear cluster. Specific DNA recognition requires residues located within as well as C terminal to this binuclear cluster. {sup 1}H NMR sequential assignments have been carried out on Zn(II){sub 2{minus}}- and {sup 113}Cd(II){sub 2}GAL4(62*) by using DQF-COSY, relayed COSY, double-relayed COSY, and NOESY. The ligands of the two tetrahedral metal-binding sites have been identified as Cys{sup 11}, Cys{sup 14}, Cys{sup 21}, and Cys{sup 31} to one metal ion and Cys{sup 28},more » Cys{sup 38}, Cys{sup 21}, and Cys{sup 31} to the other metal ion with Cys{sup 21} and Cys{sup 31} as ligands shared between the two metal ions. No {alpha}-helices can be found within the GAL4(62*) structure, which consists of a series of turns to accommodate the metal cluster, followed by irregular loops and turns from residues 42 to 60, the specificity region, whose sequence contributes importantly to specific DNA recognition. Long-distance NOE's are observed between residues forming the binuclear cluster and several residues within the specificity region, indicating that the latter is folded compactly onto the metal cluster. The requirement of the Zn(II){sub 2}Cys{sub 6} binuclear cluster and the specificity region for binding to DNA reveals GAL4 as a member of a class of specific DNA-binding proteins using a new structural motif for the recognition of specific DNA sequences. Specific DNA binding by this class of proteins is achieved by use of turns and loops that enclose a Zn(II){sub 2}Cys{sub 6} binuclear cluster, instead of {alpha}-helices or {beta}-strands as observed in specific DNA-binding proteins described previously.« less
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