|
" Hierarchy of Pyrophosphate-Functionalized Uranyl Peroxide Nanocluster Synthesis. "
Dembowski, Mateusz; Colla, Christopher A; Hickam, Sarah; Oliveri, Anna F; Szymanowski, Jennifer ES; Oliver, Allen G; Casey, William H; Burns, Peter C
| Document Type
|
:
|
AL
|
| Record Number
|
:
|
911511
|
| Doc. No
|
:
|
LA5rk6k20z
|
| Title & Author
|
:
|
Hierarchy of Pyrophosphate-Functionalized Uranyl Peroxide Nanocluster Synthesis. [Article]\ Dembowski, Mateusz; Colla, Christopher A; Hickam, Sarah; Oliveri, Anna F; Szymanowski, Jennifer ES; Oliver, Allen G; Casey, William H; Burns, Peter C
|
| Date
|
:
|
2017
|
| Title of Periodical
|
:
|
UC Davis
|
| Abstract
|
:
|
Herein, we report a new salt of a pyrophosphate-functionalized uranyl peroxide nanocluster {U24Pp12} (1) exhibiting Oh molecular symmetry both in the solid and solution. Study of the system yielding 1 across a wide range of pH by single-crystal X-ray diffraction, small-angle X-ray scattering, and a combination of traditional 31P and diffusion-ordered spectroscopy (DOSY) NMR affords unprecedented insight into the amphoteric chemistry of this uranyl peroxide system. Key results include formation of a rare binary {U24}·{U24Pp12} (3) system observed under alkaline conditions, and evidence of acid-promoted decomposition of {U24Pp12} (1) followed by spatial rearrangement and condensation of {U4} building blocks into the {U32Pp16} (2) cluster. Furthermore, 31P DOSY NMR measurements performed on saturated solutions containing crystalline {U32Pp16} show only trace amounts (∼2% relative abundance) of the intact form of this cluster, suggesting a complex interconversion of {U24Pp12}, {U32Pp16}, and {U4Pp4-x} ions.
|
| |