The first 3D malonate bridged copper [Cu(O{sub 2}C-CH{sub 2}-CO{sub 2}H){sub 2}{center_dot}2H{sub 2}O]: Structure, properties and electronic structure

Journal Article · Thu Mar 15 04:00:00 EDT 2012 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2011.11.044· OSTI ID:22012032

Seguatni, A ^[1]; Fakhfakh, M ^[2]; Smiri, L S ^[2]; Gressier, P; Boucher, F ^[3]; Jouini, N ^[4]

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1. LBPC-INSERM U 698, Institut Galilee, Universite Paris XIII, 99, avenue J. B. Clement 93430, Villetaneuse (France)
2. Unite de recherche UR 12-30, Synthese et Structure de Materiaux Inorganiques, Faculte des Sciences de Bizerte, 7021 Zarzouna (Tunisia)
3. Institut des Materiaux Jean Rouxel, Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France)
4. Departement de Chimie, Universite du Quebec a Montreal, C.P. 8888, Succ. Centre-ville, Montreal, Que., H3C 3P8 (Canada)

A new inorganic-organic compound [Cu(O{sub 2}C-CH{sub 2}-CO{sub 2}H){sub 2}{center_dot}2H{sub 2}O] ([Cumal]) was hydrothermally synthesized and characterized by IR spectroscopy, thermal analysis and single crystal X-ray diffraction. [Cumal] is the first three-dimensional compound existing in the system Cu(II)-malonic acid-H{sub 2}O. Its framework is built up through carboxyl bridged copper where CuO{sub 6} octahedra are elongated with an almost D{sub 4h} symmetry (4+2) due to the Jahn-Teller effect. The magnetic properties were studied by measuring its magnetic susceptibility in the temperature range of 2-300 K indicating the existence of weak ferromagnetic interactions. The electronic structure of [Cumal] was calculated within the density functional theory (DFT) framework. Structural features are well reproduced using DFT structural optimizations and the optical spectra, calculated within the dielectric formalism, explain very well the light blue colour of the compound. It is shown that a GGA+U approach with a U{sub eff} value of about 6 eV is necessary for a better correlation with the experiment. - Graphical abstract: [Cu(O{sub 2}C-CH{sub 2}-CO{sub 2}H){sub 2}{center_dot}2H{sub 2}O]: the first 3D hybrid organic-inorganic compound built up carboxyl groups. The network presents a diamond-like structure achieved via carboxyl. Highlights: Black-Right-Pointing-Pointer A new organic-inorganic material with an unprecedented topology is synthesized. Black-Right-Pointing-Pointer Crystallographic structure is determined using single crystal X-ray diffraction. Black-Right-Pointing-Pointer Electronic structure is obtained from DFT, GGA+U calculation. Black-Right-Pointing-Pointer Framework can be described as formed from CuC{sub 4} tetrahedron sharing four corners. Black-Right-Pointing-Pointer This structure can be classified as an extended diamond structure.

• OSTI ID: 22012032
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Vol. . 187; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COPPER
CORRELATIONS
CRYSTALLOGRAPHY
DENSITY FUNCTIONAL METHOD
DIAMONDS
DIELECTRIC MATERIALS
ELECTRONIC STRUCTURE
HYBRIDIZATION
HYDROTHERMAL SYNTHESIS
INFRARED SPECTRA
INORGANIC COMPOUNDS
INTERACTIONS
JAHN-TELLER EFFECT
MAGNETIC SUSCEPTIBILITY
MALONIC ACID
MONOCRYSTALS
TEMPERATURE RANGE
THERMAL ANALYSIS
TOPOLOGY
X-RAY DIFFRACTION