Zinc di(tert-butyl)phosphate complexes as precursors to zinc phosphates. Manipulation of zincophosphate structures
- Univ. of California, Berkeley, CA (United States)
- Univ. of Delaware, Newark, DE (United States)
The reaction of ZnEt{sub 2} with HO(O)P(O{sup t}Bu) gives the insoluble polymer (Zn[O{sub 2}P(O{sup t}Bu){sub 2}]{sub 2}){sub n} (1). In the presence of slight amounts of water, this reaction produces good yields of the oxo-centered tetranuclear cluster Zn{sub 4}({mu}{sub 4}-O)[O{sub 2}P(O{sup t}Bu){sub 2}]{sub 6} (2), which has been characterized by X-ray crystallography. Compound 2 is thermally labile and eliminates isobutene and water over the temperature range 130-220 {degrees}C. The ceramic yield at 900 {degrees}C corresponds to the theoretical yield for a Zn{sub 4}P{sub 6}O{sub 19} material, and the observed products at this temperature are {alpha}-Zn{sub 2}P{sub 2}O{sub 7} and {beta}-Zn(PO{sub 3}){sub 2} (by XRD). When heated in ethanol at 85 {degrees}C for 30 h, 2 converts to polymer 1 and ZnO. This transformation is facilitated by acids, which allow the conversion to occur at room temperature. Polymer 1, characterized by X-ray crystallography, adopts a zigzag structure with zinc atoms linked alternately by one and then three bridging phosphate groups. This structure is therefore different from that adopted by the other two organozincophosphate (Zn[O{sub 2}P(OR){sub 2}]{sub 2}){sub n} polymers that are known, which exist as linear chains with the zinc atoms bridged by two phosphate groups. 24 refs., 9 figs., 7 tabs.
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 526078
- Journal Information:
- Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 1 Vol. 9; ISSN CMATEX; ISSN 0897-4756
- Country of Publication:
- United States
- Language:
- English
Similar Records
Molecular and polymer precursor routes to manganese-doped zinc orthosilicate phosphors
Di(tert-butyl) phosphate complexes of aluminum: Precursors to aluminum phosphate xerogels and thin films