Hydrothermal syntheses, crystal structures and properties of 0-D, 1-D and 2-D organic-inorganic hybrid borotungstates constructed from Keggin-type heteropolyanion [alpha-BW{sub 12}O{sub 40}]{sup 5-} and transition-metal complexes

Journal Article · Wed Jul 15 00:00:00 EDT 2009 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.04.028· OSTI ID:21370486

Junwei, Zhao; Yiping, Song; Pengtao, Ma ^[1]

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1. Institute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004 (China)

Three novel organic-inorganic hybrid borotungstates {l_brace}[Ni(phen){sub 2}(H{sub 2}O)]{sub 2}H(alpha-BW{sub 12}O{sub 40}){r_brace}.4H{sub 2}O (1), [Cu{sup I}(2,2'-bipy)(4,4'-bipy){sub 0.5}]{sub 2}{l_brace}[Cu{sup I}(2,2'-bipy)]{sub 2}Cu{sup I}(4,4'-bipy){sub 2} (alpha-BW{sub 12}O{sub 40}){r_brace} (2) and {l_brace}[Cu{sup I}(4,4'-bipy)]{sub 3}H{sub 2}(alpha-BW{sub 12}O{sub 40}){r_brace}.3.5H{sub 2}O (3) (phen=1,10-phenanthroline, 2,2'-bipy=2,2'-bipyridine, 4,4'-bipy=4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized by elemental analyses, IR, UV spectra, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), single-crystal X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and photoluminescence. The structural analysis reveals that 1 consists of a 0-D bisupporting polyoxometalate cluster where two [Ni(phen){sub 2}(H{sub 2}O)]{sup 2+} cations are grafted on the polyoxoanion [alpha-BW{sub 12}O{sub 40}]{sup 5-} through two terminal oxygen atoms, 2 shows a 1-D infinite chain constructed from [alpha-BW{sub 12}O{sub 40}]{sup 5-} polyoxoanions and {l_brace}[Cu{sup I}(2,2'-bipy)]{sub 2}Cu{sup I}(4,4'-bipy){sub 2}{r_brace}{sup 3+} cations by means of alternating fashion, and 3 displays an unprecedented 2D extended structure built by [alpha-BW{sub 12}O{sub 40}]{sup 5-} polyoxoanions and -Cu{sup I}-4,4'-bipy- linear chains, in which each [alpha-BW{sub 12}O{sub 40}]{sup 5-} polyoxoanion acts as a tetradentate inorganic ligand and provides three terminal oxygen atom and one two-bridging oxygen atom. The presence of Ni{sup II} and W{sup VI} in 1, Cu{sup I} ions and W{sup VI} in 2 and 3 are identified by XPS spectra. The photoluminescence of 2 and 3 are also investigated. - Graphical abstract: Three novel organic-inorganic hybrid borotungstates {l_brace}[Ni(phen){sub 2}(H{sub 2}O)]{sub 2}H(alpha-BW{sub 12}O{sub 40}){r_brace}.4H{sub 2}O (1), [Cu{sup I}(2,2'-bipy) (4,4'-bipy){sub 0.5}]{sub 2}{l_brace}[Cu{sup I}(2,2'-bipy)]{sub 2}Cu{sup I}(4,4'-bipy){sub 2}(alpha-BW{sub 12}O{sub 40}){r_brace} (2) and {l_brace}[Cu{sup I}(4,4'-bipy)]{sub 3}H{sub 2}(alpha-BW{sub 12}O{sub 40}){r_brace}.3.5H{sub 2}O (3) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analyses, X-ray photoelectron spectroscopy and photoluminescence.

• OSTI ID: 21370486
• Journal Information: Journal of Solid State Chemistry, Vol. 182, Issue 7; Other Information: DOI: 10.1016/j.jssc.2009.04.028; PII: S0022-4596(09)00186-8; Copyright (c) 2009 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
BIPYRIDINES
BORON COMPOUNDS
COPPER COMPLEXES
CRYSTAL STRUCTURE
HYDROTHERMAL SYNTHESIS
INFRARED SPECTRA
PHENANTHROLINES
PHOTOLUMINESCENCE
THERMAL GRAVIMETRIC ANALYSIS
TUNGSTATES
ULTRAVIOLET SPECTRA
X-RAY DIFFRACTION
X-RAY PHOTOELECTRON SPECTROSCOPY
AROMATICS
AZAARENES
AZINES
CHEMICAL ANALYSIS
COHERENT SCATTERING
COMPLEXES
DIFFRACTION
ELECTRON SPECTROSCOPY
EMISSION
GRAVIMETRIC ANALYSIS
HETEROCYCLIC COMPOUNDS
LUMINESCENCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PHOTON EMISSION
PYRIDINES
QUANTITATIVE CHEMICAL ANALYSIS
REFRACTORY METAL COMPOUNDS
SCATTERING
SPECTRA
SPECTROSCOPY
SYNTHESIS
THERMAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
TUNGSTEN COMPOUNDS