Synthesis and photochemical properties of porous zirconium viologen phosphonate compounds

Journal Article · Fri Dec 31 23:00:00 EST 1993 · Chemistry of Materials; (United States)

DOI:https://doi.org/10.1021/cm00037a017· OSTI ID:6834900

Vermeulen, L A; Thompson, M E ^[1]

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1. Princeton Univ., Princeton, NJ (United States)

The authors recently reported stable, photoinduced charge separation in layered zirconium phosphonate viologen compounds (Zr(O[sub 3]PCH[sub 2]CH[sub 2](bipyridinium)CH[sub 2]CH[sub 2]PO[sub 3])X[sub 2] (X = Cl, Br, I), ZrPV (X)). Here, they report the synthesis and photochemical properties of porous versions of this material. Porosity can be built into the material by preparing a layered solid from a mixture of the large viologen bisphosphonic acid and a smaller phosphorus acid (i.e., Zr(O[sub 3]P-R)[sub 1](O[sub 3]PCH[sub 2]CH[sub 2](bipyridinium)CH[sub 2]CH[sub 2]PO[sub 3])[sub 0.5]C; R = O[sup [minus]], OH, H, alkyl). These materials were characterized by powder X-ray diffraction and IR and NMR spectroscopies. The resulting structures are microporous and undergo photoreduction of the viologen at a faster rate than in ZrPV (X) compounds. Evidence for the porosity in these mixed materials is seen in the air sensitivity of the photoreduced species. Photoreduction of the viologen groups is observed only under anaerobic conditions, and the photoreduced solid is bleached immediately and quantitatively in the air. In contrast the close-packed analogs (ZrPV(X)) can be photoreduced and are moderately stable in the air. Detailed photophysical and isotopic labeling studies suggest that the mechanism for photoreduction of viologen in these materials is similar to that proposed for ZrPV(X). 21 refs., 5 figs.

• OSTI ID: 6834900
• Journal Information: Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 6:1; ISSN CMATEX; ISSN 0897-4756
• Country of Publication: United States
• Language: English

Related Subjects

14 SOLAR ENERGY
140505 -- Solar Energy Conversion-- Photochemical
Photobiological
& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ABSORPTION SPECTROSCOPY
AZINES
BIPYRIDINES
CHEMICAL PREPARATION
CHEMISTRY
COHERENT SCATTERING
DIFFRACTION
HETEROCYCLIC COMPOUNDS
LABELLING
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHONATES
PHOTOCHEMISTRY
POROSITY
PYRIDINES
RESONANCE
SCATTERING
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
X-RAY DIFFRACTION
ZIRCONIUM COMPOUNDS