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Synthesis and Characterization of Cerium-Oxo Clusters Capped by Acetylacetonate

Cite this: Inorg. Chem. 2024, 63, 21, 9406–9417
Publication Date (Web):October 4, 2023
https://doi.org/10.1021/acs.inorgchem.3c02141

Copyright © 2023 The Authors. Published by American Chemical Society. This publication is licensed under

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Abstract

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 cerium-acetylacetonate (acac1–) monomeric molecule, Ce(acac)4 (Ce-1), and two acac1–-decorated cerium-oxo clusters, [Ce10O8(acac)14(CH3O)6(CH3OH)2]·10.5MeOH (Ce-10) and [Ce12O12(OH)4(acac)16(CH3COO)2]·6(CH3CN) (Ce-12), were prepared and structurally characterized. The Ce(acac)4 monomer contains CeIV. Crystallographic data and bond valence summation values for the Ce-10 and Ce-12 clusters are consistent with both clusters having a mixture of CeIII and CeIV cations. Ce L3-edge X-ray absorption spectroscopy, performed on Ce-10, showed contributions from both CeIII and CeIV. The Ce-10 cluster is built from a hexameric cluster, with six CeIV sites, that is capped by two dimeric CeIII units. By comparison, Ce-12, which formed upon dissolution of Ce-10 in acetonitrile, consists of a central decamer built from edge sharing CeIV hexameric units, and two monomeric CeIII sites that are bound on the outer corners of the inner Ce10 core. Electrospray ionization mass spectrometry data for solutions prepared by dissolving Ce-10 in acetonitrile showed that the major ions could be attributed to Ce10 clusters that differed primarily in the number of acac1–, OH1–, MeO1–, and O2– ligands. Small angle X-ray scattering measurements for Ce-10 dissolved in acetonitrile showed structural units slightly larger than either Ce10 or Ce12 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 Ce10 and Ce12 reported herein.

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SPECIAL ISSUE

This article is part of the Ligand-Metal Complementarity in Rare Earth and Actinide Chemistry special issue.

Synopsis

The synthesis and solid-state structural chemistry of a ceriumIV-acetylacetonate monomeric unit, and two unique ceriumIII/IV-oxo clusters, Ce10 and Ce12, are described. The solution stability of Ce10 was examined using electrospray ionization mass spectrometry, small-angle X-ray scattering, and NMR spectroscopy. While the cluster readily forms from methanolic solutions, dissolution in acetonitrile likely results in aggregation into average larger species in solution, and, ultimately, precipitation of Ce12.

Introduction

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Cerium-based materials have found application in areas ranging from catalysis to downconverters in light emitting diodes. (1−7) These applications, together with the relative abundance and low cost of cerium, have motivated efforts focused on structure–property relationships and hence materials development. Among cerium compounds, CeO2 (ceria) stands out as having uniquely diverse properties. One of the most notable industrial applications of ceria is its use in three-way catalysts (TWCs); ceria can serve several purposes for TWCs, including acting as an oxygen storage component due to its reduction potential. (8,9) In fact, the accessibility of the +3 and +4 oxidation states prompts many efforts that seek to harness the redox chemistry of cerium toward uses in optics, solid-oxide fuels, and oxygen storage. (10−12) Largely motivated to (1) better understand the catalytic behavior of CeO2 and (2) develop novel Ce-based catalysts that can be fine-tuned for specific applications, the chemistry community has become interested in cerium-oxo clusters. These species can be regarded as molecular scale nanoparticles of CeO2, and their properties seem to depend on the nuclearity and composition of the Ce cluster. (13) As a testament, Christou et al. recently demonstrated the ability of Ce-oxo clusters to scavenge reactive oxygen species, and the activity of these clusters was dependent on the number of CeIII atoms present in the cluster. (14) It seems likely that the catalysis applications space for Ce-oxo clusters is wide and diverse because there are a large number of Ce-oxo clusters that can be prepared. For example, synthetic chemists have discovered reproducible synthetic methods for molecules that have between two cerium atoms (homometallic dimers; Ce2) and clusters with up to one hundred cerium atoms (Ce100). In an attempt to further diversify the landscape of Ce-oxo cluster chemistry, new avenues in Ce-oxo cluster synthesis are currently being explored by many research teams. (6,14−25)
In addition to serving as a platform for realizing novel materials properties, Ce-oxo clusters may also provide important insight into the chemical behavior of the lower valent actinides. (26,27) Cerium has historically served as a surrogate for plutonium, owing to similarities in ionic radii and accessible +3 and +4 oxidation states. (28−32) Specifically regarding cluster chemistry, there are several phases, including the M6-, M22-, and M38-oxo clusters, that have been isolated for both Ce and Pu ions. (20,24,25,33−35) Similarities between Ce and Pu suggest that Ce may serve as a potential guide for expanding Pu cluster chemistry. The latter is significant because nanosized Pu-oxo cluster chemistry is of potential relevancy for plutonium processing chemistry and fate and transport in the environment. (36−39) In this regard, defining Ce-oxo cluster chemistry will advance our overall understanding of lanthanide vs actinide cluster chemistry, thereby improving our ability to control the chemistry of f-element oxo-clusters and advance our predictive capabilities in this area. Indeed, the potential translatability of Ce to actinide cluster chemistry motivates our current efforts.
Previously, our group reported the synthesis and characterization of a Ce38-oxo cluster that was isolated from halide media using K1+ counterions. (24) The compound was prepared through evaporation and exhibited a solid-state phase transformation that underscored the surface lability and reactivity of chloride ligated Ce-oxo clusters. Herein, we sought to limit synthetic challenges by controlling the surface lability and Ce redox chemistry. We achieved this control by leveraging nonaqueous alcoholic solutions and through the use of acetylacetonate (acac1–) as a bidentate cluster capping agent. Note, acac1– has been used previously in lanthanide cluster chemistry. (40,41) Toward this end, we examined reactions between cerium and acac1– in alcoholic solvents: methanol and ethanol. We then developed synthetic methodology for monomeric Ce(acac)4 as well as for two novel acac1– capped clusters: [Ce10O8(acac)14(CH3O)6(CH3OH)2]·10.5MeOH (Ce-10) and [Ce12O12(OH)4(acac)16(CH3COO)2]·6(CH3CN) (Ce-12). The structures were characterized by single-crystal X-ray diffraction. Bond valence summation values for the Ce sites (42,43) suggested that Ce(acac)4 contained CeIV, Ce-10 contained both CeIII and CeIV, and Ce-12 also contained CeIII and CeIV. Examination of Ce-10 using X-ray absorption spectroscopy (XAS) was consistent with the mixed oxidation state CeIII/CeIV formulation. The vibrational properties of the compounds are also described. The stability of the Ce-10 cluster in solution was examined via 1H NMR spectroscopy, small-angle X-ray scattering (SAXS), and electrospray ionization mass spectrometry; these data suggest that upon dissolution in acetonitrile, Ce-10 aggregates into particles with a larger average size than the Ce-10 and Ce-12 clusters. Overall, this work points to the utility of β-diketonate ligands in the isolation of Ce-oxo clusters and the importance of solvent on cluster topology. The latter is evidenced by the precipitation of monomers from ethanol, decamers from methanol, and dodecamers from acetonitrile. This observation highlights the unique solvent role in Ce-oxo formation, and we are excited at the prospect of better defining solvent effects in the following studies. Moreover, given the simplicity and facile reproducibility of the synthesis, this organic system may be an entry to differentiating cluster chemistry for plutonium and, potentially, other actinide elements.

Experimental Section

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Materials

The following chemicals were purchased from commercial suppliers and used as received: Ce(NO3)3·6H2O (ACROS Organics), acetylacetone (Hacac; TCI America), methanol (Fisher Chemical), 200 proof ethanol (The Warner-Graham Company), triethylamine (Sigma-Aldrich), acetonitrile (MeCN; Fisher Chemical), and hexanes (Fisher Chemical). All of the following reactions were performed under ambient conditions.

Synthetic Details

Compound Ce-1, Ce(acac)4, was obtained by dissolving Ce(NO3)3·6H2O (0.3262 g, 1 mmol) and Hacac (204 μL, 2 mmol) in EtOH (3 mL) in a glass vial (7 mL). The solution was sonicated for five min, and then triethylamine (557 μL, 4 mmol) was added dropwise to the solution. The solution was then cooled to 15 °C. After 1 week, orange, rod-like crystals of Ce-1 and an unidentified yellow–orange powder had precipitated. The mother liquor was removed from the vial, and the reaction product was washed (3 × 3 mL) with a one-to-one mixture of EtOH-to-hexanes. The crystals were left to dry under ambient conditions (1 h). Note that based on visual inspection and PXRD (Figure S13), Ce-1 was a minor phase in the reaction product.
Compound Ce-10, [Ce10O8(acac)14(CH3O)6(CH3OH)2]·10.5MeOH, was prepared using various synthetic conditions, as detailed in the Supporting Information. The synthesis described here is readily reproducible and yields a pure phase. Ce(NO3)3·6H2O (0.3262 g, 1 mmol) and Hacac (204 μL, 2 mmol) were added to a glass vial (7 mL) that contained MeOH (3 mL). The solution was sonicated (5 min) until the Ce(NO3)3·6H2O dissolved. Once dissolved, triethylamine (557 μL, 4 mmol) was added dropwise to yield a dark-orange solution. The solution was then capped and cooled to 15 °C. After 24 h, orange crystals formed, and the mother liquor was removed. The crystals were washed (3 × 3 mL) with a one-to-one mixture of MeOH-to-hexanes. Then the crystals were left to dry under ambient conditions (1 h). Yield based on Ce: 20%. Elemental analysis calc (obs) C: 29.60 (29.81), H: 3.89 (3.88).
Compound Ce-12, [Ce12O12(OH)4(acac)16(CH3COO)2]·6(MeCN), was obtained by combining [Ce10O8(acac)14(CH3O)4(CH3OH)4]·10.5MeOH (Ce-10, 10 mg, 0.003 mmol) and acetonitrile (0.5 mL) in a glass vial (7 mL). A yellowish–brown suspension formed after the mixture was sonicated (10 min). The vial was capped, and after 1 week, yellow single crystals (rod shaped) of Ce-12 formed alongside an unidentified light brown powder. Note that the compound is formulated with two acetate ligands that are presumed to form in situ, vide infra.

Structure Determination by Single Crystal X-ray Diffraction

Crystals of Ce-1, Ce-10, and Ce-12 were isolated from the bulk reaction products and mounted on MiTeGen loops in Paratone oil. Single crystal X-ray diffraction data were collected at 100 K on a Bruker D8 Quest diffractometer equipped with a Mo Kα microfocus source (λ = 0.71073 Å), an Oxford 700 Cryostream, and a Photon100 detector. The data were integrated using the SAINT software package included in APEX3, and absorption corrections were applied using a multiscan technique in SADABS. The structures were solved using SHELXT and refined by full matrix least-squares on F2 using SHELXL software on shelXle64. (44−48) Crystal data and structure refinement details are provided in Table 1; further details of the structure refinements are provided in the Supporting Information.
Table 1. Crystallographic Structure Refinement Details for Ce-1, Ce-10, and Ce-12
 Ce-1Ce-10Ce-12
FormulaC30H28CeO8C78 H122 Ce10 O44[C84H118Ce12O52](C2H3N)6
MW (g mol–1)536.543164.953887.54
T (K)100100100
crystal color/habitorange rodorange blockyellow block
crystal systemmonoclinicmonoclinictriclinic
λ (Å)0.710730.710730.71073
Space groupC2/cP21/nP-1
a (Å)21.5200(13)14.7545(8)14.173(5)
b (Å)8.3715(5)20.6763(11)16.254(6)
c (Å)13.9042(9)20.1617(11)16.770(9)
α (deg)9090112.390(14)
β (deg)114.353(2)108.647(2)108.333(18)
γ (deg)909098.191(13)
V (Å3)2282.0(2)5827.8(5)3236(3)
Z222
ρ (mg m–3)1.5621.8041.995
μ (mm–1)2.0353.8924.209
R10.01840.04840.0448
wR20.0950.10170.1477
GOF1.4141.0281.035
CCDC225700422570052257002

Bulk Solid-State Characterization Methods

Powder X-ray diffraction data for the bulk samples from which crystals of Ce-1, Ce-10, and Ce-12 were isolated were obtained using Cu–Kα radiation (λ = 1.542 Å) on a Rigaku Ultima IV X-ray diffractometer from 3 to 40° in 2θ with a step speed of 1 degree/min (Figures S13–S15). IR spectra for Ce-10 and Ce-12 were collected on single crystals using a Nicolet iN10 Infrared Microscope FTIR-ATR with a Ge ATR tip over Δν 675–4000 cm–1 (Figures S17–S18). For Ce-10, combustion elemental analysis was performed on the bulk sample by using a PerkinElmer model 2400 elemental analyzer.

X-ray Absorption Spectroscopy (XAS)

A sample of Ce-10, and oxidation state standards, CeO2 and Ce(acac)3·(H2O)x, were prepared as detailed in the Supporting Information. Ce L3-edge XAS data were collected in transmission mode using an in-house XAS spectrometer at Los Alamos National Laboratory. (49) Fifty scans were obtained and averaged per cerium sample, and four scans were obtained and averaged for the Cr foil (used for energy calibration). Data manipulation and analysis were conducted as previously described by Solomon and co-workers. (50) Further details on the instrument configuration, data collection, and data analysis are available in the Supporting Information.

Solution State Characterization Methods

Small Angle X-ray Scattering (SAXS)

X-ray scattering data were collected on an Anton Paar SAXS instrument using Cu–Kα radiation (1.54 Å) equipped with line collimation. A 2-D image plate was used for data collection in the q = 0.018–2.5 Å–1 range. The lower q resolution is limited by the beam attenuator. The solution obtained by dissolving Ce-10 in acetonitrile was filtered with a 0.45 μm membrane filter and then filled in a 1.5 mm glass capillary (Hampton Research) for the SAXS measurement. Scattering data of neat solvent were also collected for background subtraction. Scattering was measured for 30 min for each experiment. SAXSQUANT software was used for data collection and post processing (normalization, primary beam removal, background subtraction, desmearing, and smoothing to remove extra noise created by the desmearing routine). Data were analyzed using IRENA macros with IgorPro 6.3 (Wavemetrics) software. (51) Simulated scattering patterns of the Ce-10 and Ce-12 clusters were generated using SolX utilizing structural files (.xyz) containing a selected portion of the structure that did not include solvent or coordinated ligands. (52)

1H Nuclear Magnetic Resonance Spectroscopy

Crystals of Ce-10 were dissolved in deuterated acetonitrile (CD3CN) and filtered through Celite. A 1H NMR spectrum was then collected using a Varian 400-MR NMR. The spectrum (Figure S22) and peak assignments (Table S6) are provided as Supporting Information.

Electrospray Ionization Mass Spectrometry

Mass spectra were collected by using nanospray ionization and a quadrupole time-of-flight instrument (QStar XL, Sciex, Ontario, Canada). Crystals of Ce-10 (4.5 mg) were dissolved in acetonitrile, and the solution was diluted to approximately 50 μM. The sample solution was then loaded into a pulled borosilicate capillary (1 mm o.d. 0.75 mm i.d. pulled to 5 μm tip size) with its tip placed ∼1 cm from the curtain plate inlet of the mass spectrometer. A platinum electrode was inserted into the back of the capillary to make electrical contact with the solution for nanospray generation. Voltages of 2200–2400 V were applied to the solution while the spectrometer plate was held at 1100 V. The instrument was operated in TOF mode without any collision-induced dissociation gas in Q2 using DP1 = 50 V and DP2 = 10 V. These conditions produced a gentle ion sampling while helping desolvate the noncovalently bound solvent molecules.

Results and Discussion

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Structure Descriptions

Compound Ce-1, Ce(acac)4, crystallized in the monoclinic space group, C2/c. The structure consists of a CeIV monomeric unit, Ce(acac)4, that is composed of an eight-coordinate cerium(IV) metal center bound to oxygen atoms from four acac1– ligands as shown in Figure 1. The acac1– ligands bind in a bidentate fashion, with Ce–O bond distances ranging from 2.311(2)–2.348(2) Å. Note that Ce-1 is isostructural with a Ce(acac)4 monomer reported by Matkovic and Grdenic; (53) however, the compound crystallizes with a different unit cell.

Figure 1

Figure 1. Ball and stick illustration of the Ce(acac)4 monomer. Ce is shown in yellow, O in red, and C in black. Hydrogen atoms have been removed for clarity.

Compound Ce-10, [Ce10O8(acac)14(CH3O)6(CH3OH)2]·10.5 MeOH, crystallized in the P21/n space group. Five crystallographically unique Ce sites constitute the structure of Ce-10. Further details on metal ion coordination numbers and Ce–O bond lengths are provided in the Supporting Information (Table S2). Overall, the structure is built from a decameric [Ce6IVCe4IIIO8(OMe)4]16+ cluster core (Figure 2), wherein ten Ce sites are bridged by eight μ34-oxo dianions and four μ3-OMe1– monoanions. Bond valence summation values, which are the sum of the individual valences for an atom that add up to the oxidation state, (54) calculated for the Ce-10 cluster were consistent with six CeIV and four CeIII sites (Table S7). The CeIV sites are located at the center of the Ce10 core and adopt an oxo-bridged hexanuclear moiety with six CeIV cations connected by eight oxo-ligands; related structural units have been reported for both trivalent (e.g., Bi and Ce) and tetravalent (e.g., Zr, Hf, Th, U, Np, Pu) metal ions. (35,55−70) By comparison, the CeIII sites form methoxy-bridged dinuclear [Ce2(OMe)2] species and two of these structural units “cap” the hexamer via bridging μ4-oxo groups to generate the decameric cluster shown in Figure 2. Fourteen acac1– ligands, two OMe1–, and two MeOH ligands bind the cluster core (Figure 2b).

Figure 2

Figure 2. Illustration of the Ce10 cluster of Ce-10 (a) highlighting the [Ce6IVCe4IIIO8(Ome)4]16+ core; CeIII and CeIV sites are shown in orange and yellow, respectively, and (b) showing the acac1– decorated [Ce10O8(acac)14(CH3O)6(CH3OH)2] cluster. Ce is shown in yellow and orange, O in red, and C in black.

Dissolution of Ce-10 in acetonitrile reproducibly generated compound Ce-12, [Ce12O12(OH)4(acac)16(CH3COO)2]·6(CH3CN), which crystallized in the triclinic space group, P-1. Overall, the structure is composed of a Ce12-oxo/hydroxo cluster, [CeIV10CeIII2O12(OH)4]18+, that is ligated by 16 acac1– and two acetate groups to give a neutral cluster (Figure 3). Within the cluster, there are six crystallographically unique Ce sites, one of which (Ce1) is CeIII and five of which (Ce2–Ce6) are CeIV based on BVS values (Table S10). As shown in Figure 3a, the five CeIV metal centers, together with their symmetry equivalent sites, are bridged through two μ2-hydroxo, two μ3-hydroxo, ten μ3-oxo, and two μ4-oxo groups to form a decameric unit that can be described as two edge-sharing Ce6 octahedra. These octahedra are linked through two μ4-oxo sites. The two CeIII metal centers are located at opposite sides of the Ce10 core (related by an inversion center) to yield the Ce12 structural unit; the CeIII cations bind through two μ3-oxo ions (of the Ce10 unit), which become μ4-oxo via coordination of the CeIII sites. Location of the CeIII metal centers at the periphery of the cluster is consistent with previous reports of Ce cluster chemistry, (24,71) as well as the structure of compound Ce-10. As shown in Figure 3b, the [CeIV10CeIII2O12(OH)4]18– cluster is further coordinated to 16 acac1– and two acetate ligands, with the latter presumably forming in situ through oxidative cleavage of the acac1–. (72) Additionally, six acetonitrile molecules are present in the lattice (Figure S11). Further details on metal ion coordination numbers, Ce–O bond distances, and Ce–OH bond lengths are provided in the Supporting Information (Table S3).

Figure 3

Figure 3. Illustration of Ce-12 highlighting (a) the [CeIV10CeIII2O12(OH)4]18+ cluster core that consists of both CeIII (orange) and the CeIV (yellow) sites and (b) the acac1– and acetate decorated [Ce12O12(OH)4(acac)16(CH3COO)2] cluster. Ce is shown in yellow and orange, O in red, and C in black. Acetonitrile molecules that reside in the lattice have been omitted for clarity.

Relationship to Other Ce-Oxo Clusters

Cerium cluster chemistry has seen a significant expansion over the past two decades. (18,20,24,73−78) 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. As summarized in the Supporting Information (Table S12), the most common core motif reported for Ce is the hexameric unit of composition [Ce6O4(OH)4]12+. (14,18,24,77,79) This cluster has most frequently been isolated using carboxylate donors, and the Ce sites are usually tetravalent. Notably, the pervasiveness of the hexanuclear entity is similarly reflected in the cluster chemistry of other +3 and +4 metal ions including BiIII, ZrIV, HfIV, ThIV, UIV, NpIV, and PuIV. (35,64,65,80)
The Ce6 octahedral core manifests in both the Ce-10 and Ce-12 clusters reported herein. As noted above, the Ce10 assembly in Ce-10 consists of a central CeIV6 oxo bridged moiety that is effectively capped by two methoxy bridged CeIII dimers to generate a decamer. By comparison, Ce-12 is composed of edge-sharing CeIV octahedra; two CeIII monomers are located at opposite ends of the core. The observation of the Ce6 unit as a component of larger assemblies is similarly reflected in the literature. For example, Christou et al. recently reported (pyH)8[Ce10O4(OH)4(O3PPh)12(NO3)12] that consisted of a face capped [Ce6O4(OH)4]12+ core. (77) Additionally, Loiseau et al. reported a Ce dodecamer, [{Ce63-O)43–OH)34-O)2-Ce63-O)43OH)3}(CH3COO)13(SiW9O34)2]11–, that is perhaps best described as two hexameric units bridged via oxo groups. (81)
In addition to previously reported homometallic Ce10 decamers, (77) which exhibit different arrangements of Ce atoms as compared to Ce-10, there are few heterometallic assemblies that consist of Ce10 assemblies together with other metal ions such as Mn and Na. (20,82−84) These Ce10 cluster cores vary in the arrangement of the Ce metal centers and range from edge-sharing Ce6 octahedra to three Ce3 units surrounding a central Ce site. (20,82−84) Interestingly, the homo- and heterometallic structures that consist of edge-sharing Ce6 octahedra, such as (pyH)8[Ce10O4(OH)4(O3PPh)12(NO3)12] and [Ce10Mn14O24(O2CPh)32], adopt the same decameric unit that is observed in Ce-12. Such units have likewise been observed for the actinides. (85,86) For example, [U10O8(OH)6(PhCO2)14I4(H2O)2(MeCN)2] consists of edge-sharing octahedra. (86) Dodecameric species have previously been reported for lanthanide ions including Pr, Nd, Gd, and Dy. (87−91) Yet there are only a handful of homo- and heterometallic Ce12 units reported. (5,81,87,88,92) Perhaps most notably, Ce12(C2)3I17 adopts a similar core to that observed in compound Ce-12. (87) However, although the cluster in Ce-12 exists as an isolated structural unit, Ce12(C2)3I17 adopts extended chains with C2 units in interstitial positions.
Finally, it is worth noting the location of the CeIII and CeIV sites in the clusters. It is fairly well established in the cerium literature that for mixed oxidation state clusters, CeIII and CeIV tend to locate to the cluster surface and core, respectively. (18) Indeed, the oxidation state assignments of the Ce sites in Ce-10 and Ce-12 based on bond valence summation values are consistent with literature precedence. (71) For Ce-10, the CeIV sites form a hexanuclear core that is capped by CeIII dimers. Compound Ce-12 has a similar arrangement of CeIII and CeIV sites, with ten CeIV forming edge-sharing octahedra, and two CeIII located at the periphery of the cluster. This tendency is also manifested in heterometallic clusters. For example, Gupta et al. characterized [Ce6Mn12O17(O2CPh)26], which consisted of four {Mn33-O)2} surrounding a CeIV6 core. (93) Likewise, Thuijs et al. reported [Ce3Mn8O8(O2CPh)18(HO2CPh)2] for which the central position in the cluster core was occupied by CeIV and the surface was composed of two CeIII and eight MnIII sites. (94) Nonetheless, it is important to note that this is not the only arrangement observed. For example, Kögerler et al. reported a Ce decamer that consisted of CeIV cations surrounding a central CeIII. (20)

Synthetic Considerations

An interesting attribute associated with the formation of Ce-10 was that its formation was dependent on the solvent identity and the cerium starting material used in the reaction. For example, monomeric Ce(acac)4 was isolated from ethanolic solutions. Meanwhile, Ce-10 that consists of methoxy bridged units was isolated from methanolic solutions. We rationalized these results based on the realization that methanol is more acidic than ethanol, which can explain why a methoxide is formed and the ethoxide equivalent does not form. (95) Interestingly, the Ce-10 cluster was pervasive across a range of reaction conditions as detailed in the Supporting Information. The structural unit was found to precipitate irrespective of the Ce source. For example, CeIII-chloride, nitrate, triflate, and sulfate salts as well as CeIV(SO4)2 all generated the Ce-10 cluster. Thus, Ce-10 formed irrespective of the Ce oxidation state in the starting materials, with oxidation of CeIII possibly occurring by action of ambient O2, (96) and reduction of CeIV plausibly occurring via oxidation of acac1–, as reported previously. (97,98) In addition to Ce-10, two other structures built from Ce-10 were isolated (see Supporting Information). These phases differ primarily in packing due to differences in solvent inclusion into the lattice. Finally, Ce-12 was prepared through dissolution of Ce-10 in MeCN, and efforts to synthesize the phase from cerium salts were unsuccessful. The 1H NMR and SAXS data are consistent with rearrangement of the structural units in solution and ligand dissociation from the cluster. Peaks in the 1H NMR spectrum (Figure S22; Table S6) are observed at approximately 3.6, 5.45, and 5.6 ppm and are attributed to free Hacac (3.6 and 5.6 ppm) and bound acac1– (5.45 ppm, 5.6 ppm). (99) The presence of acetate ligands in Ce-12 may result from oxidative cleavage of acac1–, in situ. Such oxidative cleavage has previously been reported in MeCN using mild catalysts such as quaternary ammonium iodide and H2O2. (72) The oxidative cleavage of acac1– to yield acetate in this work points to the reactivity of the Ce clusters.

Vibrational Spectroscopy

The infrared (IR) spectra for Ce-10 (Figure S20) and Ce-12 (Figure S21) are reported. The spectra are dominated by vibrations attributed to acac1–. Assignments are provided in Tables S4 and S5.

1H Nuclear Magnetic Resonance Spectroscopy

A 1H NMR spectrum was collected for the solution obtained by adding Ce-10 to deuterated acetonitrile (Figure S22), mimicking the procedure used to obtain Ce-12. The peak observed at approximately 3.6 ppm is consistent with the keto form of free Hacac, and the peak at 5.45 ppm is assigned to bound acac1–. The peak at approximately 5.6 ppm may be attributed to the enol tautomer of Hacac or bound acac1–. These assignments point toward evidence of ligand dissociation of Ce-10 when dissolved in solution, and SAXS, discussed below, points to species larger than Ce-10 or Ce-12 in solution. Crytals of Ce-12 precipitate from the solution, along with an amorphous material that is likely cerium oxyhydroxide.

Small Angle X-ray Scattering (SAXS)

We conducted SAXS experiments to determine if any information could be gleaned about the stability of Ce-10 in acetonitrile and/or the formation of Ce-12, which (along with amorphous precipitate) was deposited from the MeCN solution of Ce-10. Certainly, rearrangement is necessary given the differences in topology and the differences in the CeIV:CeIII ratio of Ce-10 and Ce-12. Comparison of the experimental scattering data for the Ce-10/MeCN solution and the simulated scattering for both Ce-10 and Ce-12 suggest that Ce-10 reacts in MeCN to make clusters that are larger than Ce-10 and Ce-12. As shown in Figure 4a, the simulated scattering curves of Ce-10 and Ce-12 are similar given the similar size and shape of the clusters. Yet the simulated scattering curve for Ce-10 suggests a slightly larger size (based on the slight shift to lower q of the Guinier elbow at q ≈ 0.32 Å–1), despite its smaller nuclearity. In fact, for Ce-12, the distance between the periphery CeIII ions is 10.8 Å. On the other hand, comparing the longest Ce–Ce distance within the Ce10 core of Ce-12 (8.2 Å) to the longest Ce–Ce distance of Ce-10 (9.3 Å) shows that the Ce-10 core is actually bigger. This is because the Ce-10 core contains six CeIV and four CeIII, while the Ce-12 core contains ten CeIV, with commensurate shorter Ce–O bond distances, on average. Clearly there is a mismatch in the Guinier region between the experimental scattering and the simulated scattering for both Ce-10 and Ce-12; the experimental scattering shows a shift to lower q, indicating a larger average size species than both of the crystallized clusters or some aggregation. Fourier transform of the scattering data gives a pair distance distribution function (PDDF) representation (Figures 4b and S19), which is a probability distribution map of scattering vectors through the scattering species, and also provide shape information based on characteristic PDDF profiles. (100)

Figure 4

Figure 4. (a) Scattering spectra from Ce-10 dissolved in acetonitrile, along with simulated scattering for Ce-10 and Ce-12. (b) Pair distance distribution function (PDDF) of the experimental and simulated scattering data.

The PDDFs of the simulated Ce-10 and Ce-12 give Gaussian distribution of scattering vectors, as expected for approximately spherical, dense particles, and respective radii of gyration (Rg) of 4.15 and 4.05 Å (Figure S19). Rg is the size-independent, root–mean–squared average of the electrons from the center of the cluster, similar to the radius and related by ∼√(5/3)Rg = radius for a spherical particle. The distance (R) where the probability goes to zero is ∼11 Å for both Ce-10 and Ce-12, consistent with the longest Ce–O distance within the cluster core. On the other hand, the PDDF for Ce-10 dissolved in acetonitrile is consistent with the presence of clusters associated as dimers in solution, and an average Rg of 6.9 Å. (100) This sort of association is reminiscent of V10 dimerization via H-bonding, observed by SAXS in solution (also observed in the solid state). (101) Because the acac1– ligands are noted to dissociate from the cluster core via 1H NMR in acetonitrile, we suspect the SAXS data indicates that cluster–cluster association in solution is important to the Ce-10 to Ce-12 conversion.

Electrospray Ionization Mass Spectrometry (ESI-MS)

To further interrogate the identity of the Ce species present in solution upon the dissolution of Ce-10 in MeCN, ESI-MS data were collected (Figure 5). Ions above 600 m/z were attributed to Ce clusters based on isotopic patterns. Three prominent groups of peaks were observed in the spectrum: peaks around m/z 950, around m/z 1490, and around m/z 3080 corresponded to triply, doubly, and singly charged ions, respectively, based on isotopic pattern spacings. Examination of the ions within these groups showed peaks that were spaced by mass differences corresponding to water and methanol. This was interpreted as the presence of clusters that differed in the number of OH, MeO, and O2– ligands. To find potential molecular formulas, a combinatorial search was conducted using constraints of 5–15 cerium nuclearity, 7–30 acac ligands, 0–20 OH ligands, 0–20 O2– ligands, and 0–20 MeO ligands. Only formulas that satisfied the ion charge (based on a combination of CeIII and CeIV) and were within 30 ppm of the experimental monoisotopic mass were retained.

Figure 5

Figure 5. Mass spectra from 600 to 3600 m/z of 50 μM Ce-10 in a MeCN solution. The boxes with dotted lines highlight the singly, doubly, and triply charged groups of ions. The inset shows the major triply charged ion with a monoisotopic peak at m/z 948.87, with the experimental data from the Ce-10 solution in blue and the simulated data of Core Ce-10(3+) in red.

For the major triply charged ion with monoisotopic peak at m/z 948.87 (Figure 5 inset), the constraints above resulted in 14 formulas, among which 3 were Ce11 and 11 were Ce10, indicating more likelihood of Ce10 clusters. Moreover, Ce11 clusters in the original list of 14 had poorer isotopic matching with the experimental data compared to that of Ce10 clusters. Further filtering the list using a constraint of 6 CeIV centers based on crystallographic data resulted in 4 formulas, all of which were Ce10 clusters (Table S11). Accordingly, it was concluded that the triply charged ion at m/z 948.8753 represents a Ce10 cluster. The inset of Figure 5 depicts isotopic envelope matching between the experimental data and one of the 4 potential formulas: Ce10(CH3COCHCOCH3)12(OH)5O7(CH3O)23+ denoted as Core Ce-10(3+). The doubly and singly charged ion groups in Figure 5 can be interpreted in relation to the triply charged ion at m/z 948.8753 via variations in number of ligands and are further discussed in the Supporting Information (Figures S23–S25).

X-ray Absorption Spectroscopy (XAS)

Ce-10 was examined via Ce L3-edge X-ray absorption spectroscopy (XAS). Note that limited sample size or impurities precluded similar investigations for Ce-1 and Ce-12. The data were comparatively evaluated against two oxidation state standards: ceria (CeIVO2) and cerium(III) acetylacetonate [CeIII(acac)3] (Figure 6a). The spectrum from Ce-10 was hybridic in nature, meaning that it had attributes associated with both oxidation state standard extremes. It showed the double white line characteristic of cerium in a +4 oxidation state. However, the rising edge inflection point 5724.1(1) eV and peak maximum 5726.7(1) eV for the first feature were lower in energy than we expected for a CeIV complex and suggested CeIII. Another metric for deciphering CeIII vs CeIV content was the branching ratio between the two absorption features of the double white line peak: (LowEnergyFeatureIntensityLowEnergyFeatureIntensity+HighEnergyFeatureIntensity). (24,102−106) The +4 oxidation state standard, CeIVO2, had a branching ratio of 0.51. In contrast, the double white line branching ratio (determined via curve fitting analysis) for Ce-10 was 0.67. The high branching ratio in Ce-10 reflected that the low energy absorption feature was substantially more intense than the high energy feature. Higher branching ratios can be indicative of compounds that contain both CeIII and CeIV, which was consequently how we interpreted this spectrum. (107)

Figure 6

Figure 6. (A) Room temperature background subtracted and normalized Ce L3-edge XAS spectra (298 K) from Ce-10 (pink trace). For comparison, spectra collected under analogous conditions from +4 and +3 cerium oxidation state standards were included, namely CeIVO2 (blue trace) and CeIII(acac)3 (green trace). (B) The normalized Ce L3-edge spectrum from Ce-10 (○) and a linear combination analysis fit (purple trace) comprised contributions from the +4 and +3 cerium oxidation state standards, specifically CeIVO2 and CeIII(acac)3. Contributions from the +4 standard were 56(2)% and contributions from the +3 standard were 44(2)%. (C) Deconvolution of room temperature, background subtracted, and normalized Ce L3-edge spectra from CeO2 (top), Ce-10 (middle), and Ce(acac)3 (bottom). Experimental data (○) were overlaid on the fit (purple trace) and functions used to generate the model. These included Gaussian functions (brown, green, blue, and pink traces) used to model the X-ray absorption peaks and a step function (1:1 combination of an arctangent and error function; gray trace).

In Ce-10, there are eight oxo dianions, 14 acac1– monoanions, and six methoxide ligands; the total number of negative charges is 36. The presence of a double white line absorption feature in the Ce L3-edge X-ray absorption spectrum unambiguously refuted homovalent CeIII models of the spectrum. It was also difficult to rationalize that the XAS data could originate from a cluster that only had CeIV cations because of (1) the low energy associated with the rising edge inflection point, (2) the low energy for the first peak maximum, and (3) the relative intensities from the two features (high branching ratio). Instead, the experiments suggested that two contributions to the Ce10 XAS spectrum existed: one from cerium in the +3 oxidation state and another from cerium in the +4 oxidation state. Under the aforementioned designation (with six methoxide ligands), there was one way to charge balance and generate a neutral cluster: four CeIII and six CeIV. We fit the data from Ce-10 as a summation of spectra from the two oxidation state standards to test the validity of this description. This was achieved using the following equation:
Fit=N×Ce(acac)3(spectrum)+(1N)×CeO2(spectrum)
Here, Ce(acac)3(spectrum) was the L3-edge XAS data from Ce(acac)3, CeO2(spectrum) was the L3-edge XAS data from CeO2, and N was a linear combination mixing coefficient. The resulting model fit excellently the features, relative intensities, and overall line shape of the Ce L3-edge XAS data from Ce-10 (R-factor = 3.6%). The model consisted of a 44(2)% contribution from the +3 standard [Ce(acac)3] and 56(2)% contribution from the +4 standard CeO2 (Figure 6b). These experimentally determined +3 vs +4 contribution values were equivalent to the charge balanced description of Ce-10 mentioned above and the bond valence summation values from the structural analysis: four CeIII cations and six CeIV cations.

Conclusion

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A discrete Ce-oxo cluster, Ce10O8(acac)14(CH3O)6(CH3OH)2]·10.5 MeOH (Ce-10), and a monomeric molecule, Ce(acac)4, were isolated from methanol and ethanol solutions, respectively. Dissolution of Ce-10 in acetonitrile led to the isolation of another discrete Ce-oxo cluster, [Ce12O12(OH)4(acac)16(CH3COO)2](MeCN)6 (Ce-12). Bond valence summation performed for both clusters showed CeIII/CeIV mixed oxidation state cluster cores, with XAS data confirming this assignment for the Ce-10 cluster. The stability of Ce-10 in solution was probed using SAXS and ESI-MS. The ESI-MS exhibits peaks consistent with decanuclear (Ce10) species. SAXS identifies the presence of clusters in solution (either Ce-10 and/or Ce-12) that are associated via dispersive or hydrophobic interactions, which may be important for the conversion of Ce-10 to Ce-12. Overall, this study points to the utility of β-diketonate ligand scaffolds in stabilizing novel cluster cores and the role that solvent identity has on cluster formation. Note, in methanol, we isolated methoxy bridged polynuclear species, and in ethanol, we isolated monomeric structural units. Given ongoing interest in Ce-oxo cluster chemistry in catalysis application spaces and for advancing fundamental insight into lanthanide and actinide oxo cluster chemistry, our ongoing efforts center on identifying solution stable species and probing their chemical reactivity and catalytic behavior. Additionally, we are excited about the prospect of extending these results to actinide systems and characterizing similarities and/or differences between Ce and Pu cluster chemistry.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c02141.

  • Crystallographic refinement details, thermal ellipsoid plots, packing diagrams for Ce-1, Ce-10, and Ce-12, descriptions of Ce coordination chemistry in Ce-10 and Ce-12, powder X-ray diffraction patterns, small-angle X-ray scattering PDDF, IR and NMR spectra, bond valence summation values, XAS sample preparation, instrument configuration, data analysis, summary of previously reported homometallic cerium-oxo clusters (PDF)

Accession Codes

CCDC 22570022257006 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: + 44 1223 336033.

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

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  • Corresponding Author
  • Authors
    • Anamar Blanes-Díaz - Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, D.C. 20057, United States
    • Mohammad Shohel - Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States
    • Natalie T. Rice - Los Alamos National Laboratory (LANL), P.O. Box 1663, Los Alamos, New Mexico 87545, United States
    • Ida Piedmonte - Los Alamos National Laboratory (LANL), P.O. Box 1663, Los Alamos, New Mexico 87545, United States
    • Morgan A. McDonald - Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, D.C. 20057, United StatesOrcidhttps://orcid.org/0009-0008-5452-4463
    • Kaveh Jorabchi - Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, D.C. 20057, United StatesOrcidhttps://orcid.org/0000-0003-2569-4048
    • Stosh A. Kozimor - Los Alamos National Laboratory (LANL), P.O. Box 1663, Los Alamos, New Mexico 87545, United StatesOrcidhttps://orcid.org/0000-0001-7387-0507
    • Jeffery A. Bertke - Department of Chemistry, Georgetown University, 37th and O Streets NW, Washington, D.C. 20057, United StatesOrcidhttps://orcid.org/0000-0002-3419-5163
    • May Nyman - Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United StatesOrcidhttps://orcid.org/0000-0002-1787-0518
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was primarily supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Early Career Research Program under Award DE-SC0019190. KEK, MAM, and KJ also acknowledge support from the Georgetown University Earth Commons, EcoImpact Award. SAXS data were collected and analyzed at OSU; SM and MN are supported by the U.S. Department of Energy, National Nuclear Security Administration under Award DE-NA0003763. For XAS measurements, SAK, NTR, and IDP acknowledge the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry program (LANLE372) and LANL’s LDRD–DR project (20220054DR). In addition, SAK, NTR, and IDP are grateful to the LANL Directors Post-Doctoral Fellowship program (NTR) and the Agnew Postdoctoral Fellowship program (IDP) for support. Los Alamos National Laboratory is operated by Triad National Security, LLC, for the National Nuclear Security Administration of U.S. Department of Energy (Contract No. 89233218CNA000001).

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  • Abstract

    Figure 1

    Figure 1. Ball and stick illustration of the Ce(acac)4 monomer. Ce is shown in yellow, O in red, and C in black. Hydrogen atoms have been removed for clarity.

    Figure 2

    Figure 2. Illustration of the Ce10 cluster of Ce-10 (a) highlighting the [Ce6IVCe4IIIO8(Ome)4]16+ core; CeIII and CeIV sites are shown in orange and yellow, respectively, and (b) showing the acac1– decorated [Ce10O8(acac)14(CH3O)6(CH3OH)2] cluster. Ce is shown in yellow and orange, O in red, and C in black.

    Figure 3

    Figure 3. Illustration of Ce-12 highlighting (a) the [CeIV10CeIII2O12(OH)4]18+ cluster core that consists of both CeIII (orange) and the CeIV (yellow) sites and (b) the acac1– and acetate decorated [Ce12O12(OH)4(acac)16(CH3COO)2] cluster. Ce is shown in yellow and orange, O in red, and C in black. Acetonitrile molecules that reside in the lattice have been omitted for clarity.

    Figure 4

    Figure 4. (a) Scattering spectra from Ce-10 dissolved in acetonitrile, along with simulated scattering for Ce-10 and Ce-12. (b) Pair distance distribution function (PDDF) of the experimental and simulated scattering data.

    Figure 5

    Figure 5. Mass spectra from 600 to 3600 m/z of 50 μM Ce-10 in a MeCN solution. The boxes with dotted lines highlight the singly, doubly, and triply charged groups of ions. The inset shows the major triply charged ion with a monoisotopic peak at m/z 948.87, with the experimental data from the Ce-10 solution in blue and the simulated data of Core Ce-10(3+) in red.

    Figure 6

    Figure 6. (A) Room temperature background subtracted and normalized Ce L3-edge XAS spectra (298 K) from Ce-10 (pink trace). For comparison, spectra collected under analogous conditions from +4 and +3 cerium oxidation state standards were included, namely CeIVO2 (blue trace) and CeIII(acac)3 (green trace). (B) The normalized Ce L3-edge spectrum from Ce-10 (○) and a linear combination analysis fit (purple trace) comprised contributions from the +4 and +3 cerium oxidation state standards, specifically CeIVO2 and CeIII(acac)3. Contributions from the +4 standard were 56(2)% and contributions from the +3 standard were 44(2)%. (C) Deconvolution of room temperature, background subtracted, and normalized Ce L3-edge spectra from CeO2 (top), Ce-10 (middle), and Ce(acac)3 (bottom). Experimental data (○) were overlaid on the fit (purple trace) and functions used to generate the model. These included Gaussian functions (brown, green, blue, and pink traces) used to model the X-ray absorption peaks and a step function (1:1 combination of an arctangent and error function; gray trace).

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    • Crystallographic refinement details, thermal ellipsoid plots, packing diagrams for Ce-1, Ce-10, and Ce-12, descriptions of Ce coordination chemistry in Ce-10 and Ce-12, powder X-ray diffraction patterns, small-angle X-ray scattering PDDF, IR and NMR spectra, bond valence summation values, XAS sample preparation, instrument configuration, data analysis, summary of previously reported homometallic cerium-oxo clusters (PDF)

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