skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Molecular nanoparticles of cerium dioxide: structure-directing effect of halide ions
The use of halide ions in the synthesis of Ce/O clusters diverts the reaction to two halide-containing products: Cl − gives a new Ce 20 nuclearity with both a high 1 : 1 Ce 3+  : Ce 4+ ratio and a high percentage of (100) facet coverage, whereas F − gives a known Ce 6 nuclearity. Both products include bridging halide ions and are thus the first confirmation of non-oxo (OH − /O 2− ) anion incorporation onto the Ce/O cluster core.  more » « less
Award ID(s):
1900321 1828064
PAR ID:
10191103
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Chemical Communications
Volume:
56
Issue:
40
ISSN:
1359-7345
Page Range / eLocation ID:
5382 to 5385
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Angewandte Chemie International Edition)
    Abstract Ultra‐small nanoparticles of CeO2obtained in molecular form, so‐called molecular nanoparticles, have been limited to date to a family whose largest member is of nuclearity Ce40with a {Ce40O58} core atom count. Herein we report that a synthetic procedure has been developed to the cation [Ce100O149(OH)18(O2CPh)60(PhCO2H)12(H2O)20]16+, a member with a much higher Ce100nuclearity and a {Ce100O167} core that is more akin to the smallest ceria nanoparticles. Its crystal structure reveals it to possess a 2.4 nm size and high D2dsymmetry, and it has also allowed identification of core surface features including facet composition, the presence and location of Ce3+and H+(i.e. HO−) ions, and the binding modes of the ligand monolayer of benzoate, benzoic acid, and water ligands. 
    more » « less
  2. ; ; ; (, Angewandte Chemie)
    Abstract Ultra‐small nanoparticles of CeO2obtained in molecular form, so‐called molecular nanoparticles, have been limited to date to a family whose largest member is of nuclearity Ce40with a {Ce40O58} core atom count. Herein we report that a synthetic procedure has been developed to the cation [Ce100O149(OH)18(O2CPh)60(PhCO2H)12(H2O)20]16+, a member with a much higher Ce100nuclearity and a {Ce100O167} core that is more akin to the smallest ceria nanoparticles. Its crystal structure reveals it to possess a 2.4 nm size and high D2dsymmetry, and it has also allowed identification of core surface features including facet composition, the presence and location of Ce3+and H+(i.e. HO−) ions, and the binding modes of the ligand monolayer of benzoate, benzoic acid, and water ligands. 
    more » « less
  3. ; ; ; (, Dalton Transactions)
    Two new Ce IV /O 2− clusters, (pyH) 8 [Ce 10 O 4 (OH) 4 (O 3 PPh) 12 (NO 3 ) 12 ] (1) and [Ce 6 O 4 (OH) 4 (O 2 PPh 2 ) 4 (O 2 C t Bu) 8 ] (2), have been prepared that contain P-based ligands for the first time. They were obtained from the reaction of (NH 4 ) 2 [Ce(NO 3 ) 6 ], PhPO 3 H 2 or Ph 2 PO 2 H, and t BuCO 2 H in a 2 : 1 : 2 molar ratio in pyridine/MeOH (10 : 1 mL). Both compounds contain a {Ce 6 O 4 (OH) 4 } face-capped octahedral core, with 1 containing an additional four Ce IV on the outside to give a supertetrahedral Ce 10 topology; the {Ce 6 O 8 } unit is the smallest recognizable fragment of the fluorite structure of CeO 2 . The HO˙ radical scavenging activities of 1 and 2 were measured by UV/vis spectral monitoring of methylene blue oxidation by HO˙ radicals in the presence and absence of the Ce/O clusters, and the results compared with those for larger Ce 24 and Ce 38 molecular nanoparticles of CeO 2 prepared in previous work. 1 and 2 are both very poor HO˙ radical scavengers compared with Ce 24 and Ce 38 , a result that is consistent with reports in the literature that PO 4 3− ions inhibit the radical scavenging ability of traditional CeO 2 nanoparticles and putatively assigned to PO 4 3− binding to the surface. 
    more » « less
  4. ; ; ; ; ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract A mononuclear nonheme manganese(IV)–oxo complex binding the Ce4+ion, [(dpaq)MnIV(O)]+–Ce4+(1‐Ce4+), was synthesized by reacting [(dpaq)MnIII(OH)]+(2) with cerium ammonium nitrate (CAN).1‐Ce4+was characterized using various spectroscopic techniques, such as UV/Vis, EPR, CSI‐MS, resonance Raman, XANES, and EXAFS, showing an Mn−O bond distance of 1.69 Å with a resonance Raman band at 675 cm−1. Electron‐transfer and oxygen atom transfer reactivities of1‐Ce4+were found to be greater than those of MnIV(O) intermediates binding redox‐inactive metal ions (1‐Mn+). This study reports the first example of a redox‐active Ce4+ion‐bound MnIV‐oxo complex and its spectroscopic characterization and chemical properties. 
    more » « less
  5. ; ; ; ; (, Chemical Communications)
    Self-assembly reactions of CoII ions in the presence of the 2,2-bipyrimidine (bpym) ligand produced both a dinuclear and an octanuclear cation with the nuclearity being goverened by hydrogen-bonding versus anion-π interactions between the anions and the ligands. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email