Dicarboxylate assisted synthesis of the monoclinic heterometallic tetrathiocyanato bridged copper(II) and mercury(II) coordination polymer {l_brace}Cu[Hg(SCN){sub 4}]{r_brace}{sub n}: Synthesis, structural, vibration, luminescence, EPR studies and DFT calculations

Journal Article · Tue Feb 15 00:00:00 EST 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2010.12.012· OSTI ID:21504045

Klein, Axel ^[1]; Bakhtiari, Akbar ^[2]; Mahjoub, Ali Reza ^[3]; Pohl, Roland W.H. ^[1]

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1. Institut fuer Anorganische Chemie, Universitaet zu Koeln, Greinstrasse 6, 50939 Koeln (Germany)
2. Department of Inorganic Chemistry, Faculty of Chemistry, University of Tabriz, 5166614766 Tabriz (Iran, Islamic Republic of)
3. Department of Chemistry, School of Science, Tarbiat Modares University, P.O. Box 14155-4838 Tehran (Iran, Islamic Republic of)

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 the 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.

• OSTI ID: 21504045
• Journal Information: Journal of Solid State Chemistry, Vol. 184, Issue 2; Other Information: DOI: 10.1016/j.jssc.2010.12.012; PII: S0022-4596(10)00550-5; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER COMPLEXES
COPPER IONS
CRYSTALS
DENSITY FUNCTIONAL METHOD
ELECTRON SPIN RESONANCE
EMISSION SPECTRA
LANDE FACTOR
MERCURY COMPLEXES
MONOCLINIC LATTICES
PHOTOLUMINESCENCE
POLYMERS
POROUS MATERIALS
RAMAN SPECTRA
SEMICONDUCTOR MATERIALS
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TEMPERATURE RANGE 0273-0400 K
THIOCYANATES
X-RAY DIFFRACTION
ANTITHYROID DRUGS
CALCULATION METHODS
CARBONIC ACID DERIVATIVES
CHARGED PARTICLES
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIFFRACTION
DIMENSIONLESS NUMBERS
DRUGS
EMISSION
IONS
LUMINESCENCE
MAGNETIC RESONANCE
MATERIALS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOTON EMISSION
RESONANCE
SCATTERING
SPECTRA
TEMPERATURE RANGE
TRANSITION ELEMENT COMPLEXES
VARIATIONAL METHODS