Phosphorus-based ligand effects on the structure and radical scavenging ability of molecular nanoparticles of CeO<sub>2</sub>

Russell-Webster, Bradley; Lopez-Nieto, Javi; Abboud, Khalil A.; Christou, George

doi:10.1039/d1dt02667d

Cited by 6 publications

(11 citation statements)

References 54 publications

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“…The Ce 10 bioctahedral unit is again a recognizable small unit of the fluorite lattice and has never been previously reported in a discrete homometallic cluster, the few known Ce 10 clusters having very different structures. 45,46 However, it is of course a recognizable subunit of higher-nuclearity Ce x clusters, and it h a s a l s o b e e n s e e n i n t h e h e t e r o m e t a l l i c [Ce 10 Mn 8 O 18 (O 2 CR) 26 (H 2 O) 2 ] cluster. 34 The cation of 3 is the largest Ce/Mn cluster to date (Figure 4a).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂

et al. 2022

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The preparation of three new heterometallic clusters [Ce6Mn12O17(O2CPh)26] (1), [Ce10Mn14O24(O2CPh)32] (2), and [Ce23Mn20O48(OH)2(tbb)46(H2O)4](NO3)2 (3; tbb– = 4-tBu-benzoate) is reported. They all possess unprecedented structures with a common feature being the presence of an octahedral CeIV–oxo core: a Ce6 in 1, two edge-fused Ce6 giving a Ce10 bioctahedron in 2, or a larger Ce19 octahedron in 3. Complex 1 is the first Ce6 cluster with a central μ6-O2–. 2 and the cation of 3 are molecular nanoparticles of CeO2 (ceria) because they possess the fluorite structure of bulk ceria and are thus ultrasmall ceria nanoparticles in molecular form. The {Ce19O32} octahedral subunit of the cation of 3 had been predicted from density functional theory studies to be one of the stable fragments of the CeO2 lattice, but has never been previously synthesized in molecular chemistry. Around the Ce/O core of 1–3 is an incomplete monolayer of Mn n ions disposed as four Mn3, two Mn7, and four Mn5 units, respectively. This represents a clear structural similarity with composite (phase-separated) CeO2/MnO x mixtures where at high Ce:Mn ratios the Mn atoms segregate on the surface of CeO2 phases. Variable-temperature dc and ac magnetic susceptibility studies have revealed S = 2, S = 1/2, and S = 3/2 ground states for 1–3, respectively. Fitting of the 5.0–300 K dc data for 1 to a two-J model for an asymmetrical V-shaped Mn3 unit with no interaction between the end MnIII ions gave an excellent fit with the following values: J 1 = 5.2(3) cm–1, J 2 = −7.4(3) cm–1, and g = 1.96(2).

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Section: ■ Results and Discussionmentioning

confidence: 99%

Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂

et al. 2022

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“…Cerium cluster chemistry has seen a significant expansion over the past two decades. ,,,− The Ce-10 and Ce-12 clusters exhibit unique arrangements of Ce metal centers that previously have not been reported. Nonetheless, some features of the clusters compare well with those of other known clusters.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

Blanes-Díaz,

Shohel,

Rice

et al. 2023

Inorg. Chem.

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Cerium-oxo clusters have applications in fields ranging from catalysis to electronics and also hold the potential to inform on aspects of actinide chemistry. Toward this end, a ceriumacetylacetonate (acac 1− ) monomeric molecule, Ce(acac) 4 (Ce-1), a n d t w o a c a c 1 − -d e c o r a t e d c e r i u m -o x o c l u s t e r s , [Ce 10 O 8 (acac) 14 (CH 3 O) 6 (CH 3 OH) 2 ]•10.5MeOH (Ce-10) and [Ce 12 O 12 (OH) 4 (acac) 16 (CH 3 COO) 2 ]•6(CH 3 CN) (Ce-12), were prepared and structurally characterized. The Ce(acac) 4 monomer contains Ce IV . Crystallographic data and bond valence summation values for the Ce-10 and Ce-12 clusters are consistent with both clusters having a mixture of Ce III and Ce IV cations. Ce L 3 -edge X-ray absorption spectroscopy, performed on Ce-10, showed contributions from both Ce III and Ce IV . The Ce-10 cluster is built from a hexameric cluster, with six Ce IV sites, that is capped by two dimeric Ce III units. By comparison, Ce-12, which formed upon dissolution of Ce-10 in acetonitrile, consists of a central decamer built from edge sharing Ce IV hexameric units, and two monomeric Ce III sites that are bound on the outer corners of the inner Ce 10 core. Electrospray ionization mass spectrometry data for solutions prepared by dissolving Ce-10 in acetonitrile showed that the major ions could be attributed to Ce 10 clusters that differed primarily in the number of acac 1− , OH 1− , MeO 1− , and O 2− ligands. Small angle X-ray scattering measurements for Ce-10 dissolved in acetonitrile showed structural units slightly larger than either Ce 10 or Ce 12 in solution, likely due to aggregation. Taken together, these results suggest that the acetylacetonate supported clusters can support diverse solution-phase speciation in organic solutions that could lead to stabilization of higher order cerium containing clusters, such as cluster sizes that are greater than the Ce 10 and Ce 12 reported herein.

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“…The research group led by Professor George Christou developed a simple bottom-up method, where Ce III/V salt and small organic acid molecules react in solutions containing pyridine or its derivatives, to prepare ultra-small CeO 2 nanoparticles in Ce-oxo cluster form (from Ce 6 , 395,396 Ce 10 , 396 Ce 16 , Ce 19 , 397 Ce 20 , 395 Ce 24 , Ce 38 , and Ce 40 , 398 to the largest Ce 100 with a size of 2.4 nm 51 ). These Ce-O clusters possess a regular metal core with the fluorite structure of bulk CeO 2 and reflect critical information at atomic resolution of important surface features, helping CeO 2 nanoparticles to be better used in catalysis and other fields.…”

Section: Platonic and Archimedean Solids In Lanthanide-containing Clu...mentioning

confidence: 99%

Platonic and Archimedean solids in discrete metal-containing clusters

Luo

Dong

et al. 2023

Chem. Soc. Rev.

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Phosphorus-based ligand effects on the structure and radical scavenging ability of molecular nanoparticles of CeO₂

Abstract: Two new CeIV/O2- clusters, (pyH)8[Ce10-O4(OH)4(O3PPh)12(NO3)12] (1) and [Ce6O4(OH)4(O2PPh2)4(O2CtBu)8] (2), have been prepared that contain P-based ligands for the first time. They were obtained from the reaction of (NH4)2[Ce(NO3)6], PhPO3H2 or...

Cited by 6 publications

References 54 publications

Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂

Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

Platonic and Archimedean solids in discrete metal-containing clusters

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Phosphorus-based ligand effects on the structure and radical scavenging ability of molecular nanoparticles of CeO2

Abstract: Two new CeIV/O2- clusters, (pyH)8[Ce10-O4(OH)4(O3PPh)12(NO3)12] (1) and [Ce6O4(OH)4(O2PPh2)4(O2CtBu)8] (2), have been prepared that contain P-based ligands for the first time. They were obtained from the reaction of (NH4)2[Ce(NO3)6], PhPO3H2 or...

Cited by 6 publications

References 54 publications

MnII/III and CeIII/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO2

MnII/III and CeIII/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO2

Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

Platonic and Archimedean solids in discrete metal-containing clusters

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Phosphorus-based ligand effects on the structure and radical scavenging ability of molecular nanoparticles of CeO₂

Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂

Mn^II/III and Ce^III/IV Units Supported on an Octahedral Molecular Nanoparticle of CeO₂