supramolecular assembly of u(iv) clusters and superatoms€¦ · supramolecular assembly of u(iv)...

doi.org/10.26434/chemrxiv.11860065.v1

Supramolecular Assembly of U(IV) Clusters and SuperatomsIan Colliard, Gregory Morrosin, Hans-Conrad zur Loye, May Nyman

Submitted date: 16/02/2020 • Posted date: 19/02/2020Licence: CC BY-NC-ND 4.0Citation information: Colliard, Ian; Morrosin, Gregory; zur Loye, Hans-Conrad; Nyman, May (2020):Supramolecular Assembly of U(IV) Clusters and Superatoms. ChemRxiv. Preprint.https://doi.org/10.26434/chemrxiv.11860065.v1

Superatoms are nanometer-sized molecules or particles that can form ordered lattices, mimicking their atomiccounterparts. Hierarchical assembly of superatoms gives rise to emergent properties in superlattices ofquantum-dots, p-block clusters, and fullerenes. Here, we introduce a family of uranium-oxysulfate clusteranions whose hierarchical assembly in water is controlled by two parameters; acidity and the countercation. Inacid, larger LnIII (Ln=La-Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, whilesmaller LnIII (Ln=Er-Lu &Y;) promote linking of fourteen U6-clusters into hollow superclusters (U84superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, andinterpenetrating networks, bridged by interstitial countercations, and U6-clusters. Divalent transition metals(TM=MnII and ZnII), with no added acid, charge-balance and promote the fusion of 10 U6 and 10 U-monomersinto a wheel–shaped cluster (U70). Dissolution of U70 in organic media reveals (by small-angle Xrayscattering) that differing supramolecular assemblies are accessed, controlled by TM-linking of U70-clusters.

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Supramolecular Assembly of U(IV) Clusters and Superatoms Ian Colliard,1 Gregory Morrison,2 Hans-Conrad zur Loye2 and May Nyman1*

1Department of Chemistry, Oregon State University, Corvallis, OR 97331, USA 2Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA *correspondence: [email protected] Abstract: Superatoms are nanometer-sized molecules or particles that can form ordered lattices, mimicking their atomic counterparts. Hierarchical assembly of superatoms gives rise to emergent properties in superlattices of quantum-dots, p-block clusters, and fullerenes. Here, we introduce a family of uranium-oxysulfate cluster anions whose hierarchical assembly in water is controlled by two parameters; acidity and the countercation. In acid, larger LnIII (Ln=La-Ho) link hexamer (U6) oxoclusters into body-centered cubic frameworks, while smaller LnIII (Ln=Er-Lu &Y) promote linking of fourteen U6-clusters into hollow superclusters (U84 superatoms). U84 assembles into superlattices including cubic-closest packed, body-centered cubic, and interpenetrating networks, bridged by interstitial countercations, and U6-clusters. Divalent transition metals (TM=MnII and ZnII), with no added acid, charge-balance and promote the fusion of 10 U6 and 10 U-monomers into a wheel–shaped cluster (U70). Dissolution of U70 in organic media reveals (by small-angle X-ray scattering) that differing supramolecular assemblies are accessed, controlled by TM-linking of U70-clusters. Introduction:

Molecular fractals and supramolecular assemblies are studied to understand the underlying rules of complex assemblies and to access materials and molecules with multiscale properties. Molecular fractals are strategically synthesized via organic and coordination chemistry in metallocycles,1, 2 dendrimers,3, 4, 5 and proteins.6 Inorganic materials that exhibit multiscale structure replication via supramolecular assembly are rare. Rather, these phenomena have been observed at a non-molecular level, in the self-assembly of nanomaterials including CdSe nanorods,7 and silver nanosheets.8 Bimodal, monodisperse nanoparticles with organic capping groups, C60-fullerenes9 behave as ‘superatoms’, assembling into lattices that resemble binary compound structure types.10 In addition, semiconducting p-block Zintl-cluster anions11 (i.e. As7

3-, Al13

1-) can be assembled through counteraction linking into different structures that exhibit structure specific electronic properties.12, 13

Several inorganic and metal-organic materials that represent revolutionary discoveries are built via supramolecular assembly of polynuclear metal-oxo clusters, including synthetic zeolites and metal-organic frameworks (MOFs). The UiO-6614 MOF, widely exploited for its stability and adaptability to different applications, is built of hexanuclear, Zr6 oxo-clusters, isostructural with

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U6 (described later). A cluster building block of zeolites consists of eight corner-linked (Al,Si)O4 tetrahedra, and these clusters have been both isolated in the molecular form15, 16 and shown to self-assemble in solution17 prior to crystallization of zeolites. In between isolated polynuclear cluster molecules and infinite lattices built from such clusters, is any number of hypothetical entities; i.e. assemblies of clusters, or pre-nucleation ‘clusters of clusters’. As a rare example of these, metal organic polyhedra, MOPs, were designed and developed almost in parallel with MOFs, consisting of small cages joined by ditopic linkers.18, 19 There is no analogous inorganic molecule that represents a scale between a cluster building-block and an infinite lattice, because inorganic synthesis generally does not allow for precise size control at such a large scale.

Assembly of actinide clusters into materials is likewise of interest but far less prolific. One of the most common cluster motifs is the aforementioned hexamer [MIV

6(OH)4(O)4)]12+ (M=An including Th, U, Np, Pu, also Zr/Hf) stabilized by various carboxylate groups, triflates, selenate, and sulfate.20, 21, 22 23, 24 Researchers have synthesized MOFs and inorganic frameworks (including interpenetrating frameworks23) featuring linked Th6,23, 25, 26 U6,27, 28 and Np629 nodes. The An6 cluster is also an exact building block of AnO2. Recently, clusters ranging in nuclearity from An10-An38 have been isolated that are larger fragments of AnO2,30, 31, 32, 33, 34, 35, 36 elucidating understanding of colloidal actinide transport in the environment.37 UIV-sulfate speciation (with heterometals) is of special relevance to biogeochemical activity in uranium ore deposits, mining sites and the contaminated subsurface. Sulfur oxidizing bacteria immobilizes uranium as discrete UO2 nanoparticles38 (~2 nm) that are similar in dimensions to the clusters described herein.

Here we introduce a family of UIV-oxo-sulfate cluster superlattices. Polyoxoanion clusters assemble with lanthanide (LnIII) and transition metal (TMII) countercations, where the size and geometry of the polyanion (containing 6, 70 or 84 UIV-centers, respectively U6, U70, and U84) can be rationalized by acidity of the reaction media, and the covalency of the Ln or TM countercation (figure 1). U84, is a ‘cluster-of-clusters’ superatom, highlighted in three different superlattices with three generations of self-replicating structures, linked by LnIII, UIV-monomers and U6. U70 is a wheel-structure, unlike any prior-reported UIV-cluster, that is charge-balanced and assembled with TMII (Mn, Zn) in low-acidity media. In three different lattices, these also display complex supramolecular assembly, including sandwiching U6-units. Different bonding behavior of Zn2+ and Mn2+ to U70 in the solid-state are preserved in solution, further underlining the importance of these counterions on assembly processes. U70 and U84 are the largest tetravalent actinide (or Zr/HfIV) molecular clusters observed to date, strategically isolated with nonconventional, high-valence countercations.39

Figure 1. Summary of UIV-sulfate TM/Ln phases. Schematic summarizing the reaction of U(SO4)2 with (1) divalent transition metals charge-balancing U70 (top left), (2) large LnIII building U6-frameworks (middle), and (3) small LnIII charge-balancing U84 (right). Green and yellow polyhedra are respectively UIV-oxo and SO4

2-, black polyhedra are large LnIII-oxo and blue polyhedra are small LnIII-oxo. Details of these structures are in subsequent text and figures.

Results and discussion

All tetravalent metals, including UIV, exhibit strong hydrolysis behavior. Upon dissolution in water, the highly-charged cations bind water and deprotonate, leading to formation of oligomers, even in aqueous acid.40 The fundamental hydrolysis and condensation reactions describing this process are: 2OH- + 2[H2O-U]4+ → 2[HO-U]3+ + 2H2O→ [U-(OH)-U]7+ + H2O. We dissolved rare earth oxides in the acidic solutions to drive this reaction by the generation of hydroxide, i.e. La2O3 + 3H2O → 2La3+ + 6OH-. In-situ production of hydroxide in this manner is more controlled than adding a strong base, which promotes UO2-formation, the end-product of hydrolysis-condensation reactions. Additionally, the strongly coordinating sulfate ions in these reactions compete with the hydrolysis reactions, allowing assembly of cluster-based framework materials.

UIV-lanthanide assemblies Combining larger lanthanides, such as LaIII, leads to the assembly of frameworks

consisting of U6 that are bridged by the heterometal center. We have crystallized different arrangements of these from Ln = La – Ho. We describe the prototype La-U6 here as an example; others will be described in subsequent publications. La-U6, formulated La4U6(OH)4(O)4(SO4)12(H2O)20, crystallizes in the monoclinic space group P21/a (Table SI-1). The UIV hexamer is the typical core [U6(OH)4(O)4)]12+, exhibiting oxo-hydroxo disorder (fig. SI-1). The first U6-sulfate was reported in 1953;41 and then not again until very recently.24 The core U6-sulfate anion (figure 2a) is a recurring moiety throughout the structures described here. The charge-balancing LaIII bridge two hexamers via sulfate groups. Each U6-hexamer can be described as a distorted cube, with its six polyhedra occupying the six cube faces, and eight La located on

the cube corners (figure 2b). A framework arises from the ‘corner-to-corner’ linkages of bridging La-monomers. Due to the 3D-checkerboard linkage, La-U6 exhibits large voids that contain disordered lattice waters (figure 2c, Table SI-9).

Figure 2. Ln-U6 frameworks. a) polyhedral representation of [U6(OH)4(O)4(SO4)12]12-: UIV polyhedra are green, sulfate polyhedra are yellow, O is red spheres. b) Highlighting the linkage between LaIII (black spheres) and U6. c) Polyhedral representation of La-U6 framework, showing void channels along the b-axis. With the smaller LnIII (Er-Lu & Y) as countercations, a 2nd-generation assembly of U6 is

observed. Fourteen sulfate-bridged U6- clusters assemble into a hollow sphere; a U6 occupying the six faces and the eight corners of a cube (figure 3a-3b), totaling 84 UIV-centers, comprising a U84 superatom. The U6 of the corner positions, (blue, U6c) have 12 bridging sulfates, while the face U6 (green, U6f) possess 16 sulfates. Each U6f is linked to four U6c along the diagonals of the U84-cube face. Likewise, each U6c is linked to three U6f. Each U6f,-U6c linkage is through three bridging sulfates, reinforcing the rigid U84. We can rationalize this structure switch from lanthanide-linked U6 frameworks to U84 assemblies that occlude the LnIII counterions with a modern description of Ln-bonding that includes covalent bonding contribution from the 5d orbitals.42 Contraction of these orbitals across the series decreases the ability of Ln to participate in covalent network assembly. While LaIII disrupts linkage between U6-units, LuIII behaves more as a classic counterion in the superlattice, vide infra. Three structures displaying differentiating 3rd-generation assembly of U84 superatoms are described below.

Y-U84, formulated Y16[U6(OH)4(O)4]14(SO4)108(H2O)126.5, crystallizes in the tetragonal P4/m space group (volume = 39,627 Å3, Table SI-2). Each U84 is surrounded by twelve U84 units, resembling cubic closest packing of equal-sized spheres, defining the 3rd-generation of supramolecular assembly. U84 are bridged by YIII via the eight U6c-corners (figure 3c) and four of

the U6f-faces. YIII-monomers (7-8 coordinate) decorate and bridge the U84 clusters through sulfate bridges.

LuU-U84, formulated U4Lu12(U6(OH)4(O)4)14(SO4)110(H2O)80 crystallizes in the trigonal R-3c space group (volume = 137,813 Å3, Table SI-4). LuU-U84 can be described as a body centered cubic arrangement of U84 (figure 3d), linked by UIV monomers that are bridged by corner-sharing sulfates. Partially occupied LuIII also decorates and bridges U84 via the sulfates, but the main connectivity is defined by UIV-monomers. Notable is the multiscale replication of patterns: this linking of U84 joined by monomers at the eight corner-U6c is similar to the first structure described (La-U6), where U6 are linked by corners via LaIII-monomers.

ErU6-(U84)2, formulated U6(OH)4(O)4(H2O)12[Er16(U6(OH)4(O)4)14(SO4)111(H2O)130]2 (Table SI-3), crystallizes in the cubic space group Pn-3 (volume = 84,891 Å3). In ErU6-(U84)2, rotationally-disordered U6 (U6tet for this discussion, disorder detailed in the SI) occupies half the tetrahedral voids of closest packed U84, and links to the U6c via sulfate bridges. There are two interpenetrating tetrahedral ErU6-(U84)2 networks, shown in green and blue in figure 3e. The U84-units are also connected by ErIII-monomer-sulfate-U6f linkages (figure 3e, inset).

Figure 3. U84 and its superlattices. a). Polyhedral representation of U84. U6c (corner) are blue, U6f (face) are green, sulfate is yellow. b) Simplified representation of U84, replacing the U6 units with green (U6f) and blue (U6c) spheres. c) View of Y-U84, highlighting the cubic closest packing of the U84 superatoms, linked by Y-monomers (black spheres). d) View of LuU-U84, highlighting the body-centered cubic arrangement of U84, bridged by UIV-monomers (orange). e) Simplified representation of ErU6-(U84)2, highlighting the two diamondoid interpenetrating networks (respectively green and blue). Large spheres are U84, linked by U6 (small spheres). Each tetrahedral network is also bridged by partially-occupied ErIII (inset, red spheres linking blue network).

UIV-transition metal assemblies The addition of first row divalent transition metals (TMII, in the form of acetate salts) to

the aqueous uranium sulfate salt leads to a different cluster assembly. While 0.5 molar sulfuric acid was optimal to keep the LnIII-UIV reactants dissolved, the first row TMII can dissolve in water only. The lack of coordinating sulfate and lower acidity is conducive to more extensive hydrolysis. However, instead of yielding the end-produced UO2, TMII stabilizes and charge-balances a U70 ring with the core formula [U70(OH)36(O)64(SO4)60]4- (figure 1 and 4). MnII and ZnII analogues are introduced here, and others will be described in subsequent publications.

The U70-ring features 70 UIV centers fused by oxo/hydroxo ligands. It can be viewed as ten alternating U6 and UIV monomers (figure 4a). The U6-subunit has the typical core formula of [U6(OH)4(O)4)]12+. However, instead of twelve bridging-sulfates, it possesses only eight; four bridging the outer ring and four bridging the inner ring. The outer sulfates link to the UIV-monomer, while the inner sulfates bridge to neighboring hexamers, creating curvature. The entirety of the ring structure exhibits oxo/hydroxo disorder, determined by bond valence sum calculations (Table SI-11). All the uranium centers are 8-coordinate with the exception of the innermost uranium of the U6-units. These are 9-coordinate, due to an additional bound water. Additional terminally-bound sulfates link the rings in an offset ‘face-to-face’ manner in the different assemblages (fig. 4d).

Mn-U70, formulated Mn6U70(OH)36(O)64(SO4)64(H2O)44, crystallizes in the triclinic P-1 space group (volume = 16,367 Å3, Table SI-5). The U70-rings are stacked offset and face-to-face, approximately along the a-direction. They are linked together by both bridging sulfates and MnII-octahedra. The MnII-octahedra also join the stacks together nearly perpendicular to the stacking direction (figure 4d), leading to a fully connected framework (figure 4c) with large pores (Table SI-9).

Mn-U70 was obtained via the addition of TBACl (tetrabutylammonium chloride) to the

reaction solution, which can mediate the assembly of the U70-rings, by changing the ionic strength of the system. Without TBA+, we obtain a U70-(U6)2-U70 sandwich, Mn-(U6U70)2, formulated Mn4(H2O)16[(U6(OH)4(O)4)(H2O)9)(U70(OH)34(O)66(SO4)65(H2O)61]2. Mn-(U6U70)2 crystallizes in the triclinic P-1 space group (volume = 37,244 Å3, Table SI-6) The U70-(U6)2-U70 sandwich contains two U6-clusters on opposite sides and between two U70-rings. Four sulfates of U6 bridge to the ring on the outside, while the inner association is via hydrogen-bonding between U6 and U70 (figure 5c). The U6 pairs are disordered over five positions, consistent with the 10-fold symmetry

Figure 4. TMII-U70. a) Polyhedral representation of U70 highlighting the monomer and hexamer units. UIV monomer in blue and U6 unit in green, sulfur in yellow, oxygen in red. b) Representation of Zn-U70, emphasizing the coordination environments of Zn. The red octahedra are Zn linked to U70 via corner-sharing with sulfate. These sit just above the central cavity. The turquoise octahedra are Zn(H2O)6 that are located between U70-rings, unassociated. c) Mn-U70 and Zn-U70 highlighting the difference in cluster linking via Mn-octahedra (purple) and Zn-polyhedra (gray). d) View of Mn-U70 lattice (approximately perpendicular to the viewing direction in c.

Figure 5 U70-U6-U70 sandwich. a) View of the U70-U6-U70 sandwich stacking in Mn-(U6U70)2. Bright green polyhedra are UIV – oxo of U70 , brown polyhedra are the disordered hexamers, yellow polyhedra are sulfate. b) Approximately perpendicular view of the U70-U6-U70 sandwich stacks, showing linkage of the Mn-octahedra (purple), corner-sharing with sulfate. c) View of the five settings of the U6-cluster inside the sandwich. Only the uranium, shown in turquoise, blue, purple, brick, and chartreuse (left to right). d) Illustration of the 1/5th occupancy of U6, as pairs on opposite sides of the wheel. e) Highlighting connectivity of U6 via four sulfate bridges to the U70-rings.

of the U70 ring (figure 5c). Details describing this disorder are included in the SI. Chains of the [U70-(U6)2-U70]n run approximately along the a-axis (figure 5a and b), with similar offset of stacking found in Mn-U70. In addition, the charge-balancing MnII-monomers link the chains of rings in the opposite direction, approximately in the bc-plane, via coordination to sulfates of neighboring U70.

Zn-U70 was also obtained with the TBACl ‘mineralizer’. It is fully formulated (Zn(H2O)6)3.5Zn2.5U70(OH)36(O)64(SO4)64(H2O)54.5 and crystallizes in the triclinic P-1 space group (volume =14,801 Å3, Table SI-7). Zn-U70 presents a similar arrangement in the lattice as Mn-U70 (figure 4c). However, an important distinction is the lack of any linking of U70 between or within the stacks via Zn2+. Of the four Zn-sites, two are only fully bonded to water, and the other two bound inside the U70-ring (figure 4b). The 3d10 of ZnII configuration minimizes covalent linkage of the sulfate ligands, as recent in X-ray absorption studies.43

Small Angle X-ray Scattering. The extensive U70-MnII-U70 and minimal U70-ZnII-U70 connectivity observed in the solid-state compounds was also evidenced upon dissolution. Despite the entirely inorganic nature of the U70-ring, its aqueous synthesis, and its interconnectivity in various frameworks; it can be dissolved intact in organic media (1:3 THF: butylamine), perhaps because of the extremely low charge density of the cluster (-4 per 70 metal-centers). The small-angle scattering intensity for dissolved Zn-U70 and Mn-U70 is strong due to their large size and the presence of strongly scattering uranium (figure 6b). The average-size species for dissolved Mn-U70 is considerably larger than that for Zn-U70, indicated by the Guinier region shift to lower-q for the former. The Guinier region is the steep negative-slope at low-q (q<.0.15 Å-1 for Mn-U70; q<.0.20 Å-1 for Zn-U70). The Mn-U70 curve is ideally fit with a core-shell cylindrical model (Table SI-12, fig. SI-9) that matches well with simulated scattering data for a hypothetical stack of eight U70-rings. We can confidently say this is the main aggregate present in this solution, and that MnII links the clusters, in addition to the sulfate. Comparing the Zn-U70 scattering to the simulated U70-monomer scattering shows a good match between ~q=0.1-0.8 Å-1. Moreover, the two plateaus between ~q=0.2-0.2 Å-1 are observed in both the simulated and experimental scattering—strong evidence that the Zn-U70 solution is dominated by isolated clusters. However, the upward slope at q > 0.1 Å-1 indicates formation of aggregates. Analysis of the size distribution suggests the majority of the dissolved aggregates are around 35 Å (U70-monomers) in diameter, with a larger population of ~80 Å (ratio of U70:aggregates ~9:1, fig. 6c). Based on inspecting and simulating SAXS data for various U70-aggregates observed in the crystal structures, we propose the modest amount linking promoted by Zn is via staggered stacking rather than perfectly eclipsed, as observed for dissolved Mn-U70. The oscillations and other features at high-q (i.e. the peaks around 2 Å-1) that give information on shape and atom-atom distances are also present in both the experimental and simulated datasets. It is interesting that the eclipsed stacking that is so prevalent in the Mn-U70 solution has not been observed in solid-state structures presented here, nor in other structures we have obtained that will be reported shortly. Perhaps the butylamine stabilizes the cylindrical stacks via inverse micelle formation. This suggests other supramolecular assemblies may be accessible

via dissolution of U70 in organic media containing various TM-linkers and surfactants. This is a similar strategy used prior to create superlattices of nanoparticles.44, 45

Figure 6. X-ray scattering of dissolved U70 and Magnetic Susceptibility a) Hypothetical stack of eight U70, its simulated scattering data matches that of Mn-U70 (simulated scattering shown in blue in b). . b) Experimental scattering data for Mn-U70 (pink) and Zn-U70 (black) in 1:3 THF:butylamine solvent mixture. c) Isolated U70 (simulated scattering data in green), plus aggregate of four U70; [U70]4. Simulated scattering data for 90% U70 and 10% [U70]4 is shown in red. This approximate mixture is proposed for dissolved Zn-U70, as determined by size distribution analysis of experimental scattering data (see fig SI-10. d) Magnetic susceptibilities of La-U6, Y-U84, Zn-U70 measured under zfc conditions and an applied field of 1000 Oe.

Magnetic measurements. While magnetic ordering and frustration has been discovered in

polynuclear TM, Ln and TM-Ln single-molecule magnets,46 similar studies of An-TM/Ln have been less explored, partly due to a paucity of synthesized species. In fact, only one measurement of UIV-oxo clusters (U6)47 and very recently U38,48 has been executed. Similar to UIV-oxides, U6 and U38 exhibit transition of the 5f2 electrons from unpaired to paired with cooling. Typically, high coordination UIV-compounds (CN = 8) exhibit Curie-Weiss behavior49 whereas lower coordination numbers (CN = 6) lead to non-Curie-like behavior due to strong crystalline electric field effects.50 Recently, a Mn-UIV fluoride was described with magnetic coupling between the 3d and 5f electrons,51 piquing interest in magnetic properties of UIV-TM/Ln oxo-clusters and oxides.

Figure 6d shows the magnetic susceptibility of La-U6, Y-U84, Zn-U70, and Mn-U70 and the magnetic data is summarized in Table 1. In the first three compounds, UIV is the only magnetic ion, allowing for direct observation of the UIV magnetic behavior. All three compounds exhibit Curie-Weiss behavior at high temperatures, without pairing of the 5f2-electrons down to 2 K. Fitting the 50-300 K data to the Curie-Weiss law yields effective moments of 3.58(3) μB/U (La-U6), 3.19(3) μB/U (Y-U84), and 2.36(3) (Zn-U70). Because of the non-Curie like behavior of many UIV-compounds, the uranium moment is often estimated as 2.827(χT)1/2 at 300 K, yielding moments reported in Table 1. The observed moment for La-U6 extracted from the Curie-Weiss fit

is in excellent agreement with the calculated moment of 3.58 μB/U for UIV, and the others are within the reported ranges.52 Variations correlate with UIV-coordination. The largest is observed for La-U6, in which the majority of the UIV-sites are 9-coordinate (four of six), and the lowest is observed for Zn-U70, in which the U sites are predominately 8-coordinate (56 of 70). Y-U84, with an intermediate moment, contains almost half 8-coordinate U sites (48 of 84). All three compounds have large, negative paramagnetic Curie-Weiss temperatures, likely due to crystalline-electric field effects. The magnetic susceptibility of Mn-U70 likewise exhibits Curie-Weiss behavior at high temperatures, however no magnetic ordering is observed down to 2 K.

Table 1 Magnetic properties of reported phases. All data fit to the Curie-Weiss law from 50-300K. θ (K) μeff (μB/F.U.) μcalc (μB/F.U.) μeff (μB/U) μcalc (μB/U)

La-U6 -140(3) - - 3.58(3) 3.58

Y-U84 -112(3) - - 3.21(3) 3.58

Zn-U70 -79(2) - - 2.36(3) 3.58

Mn-U70 -28.2(6) 27.93(9) 33.28 2.85(3)a 3.58

aCalculated assuming an observed moment of 5.92 μB/Mn

The TMII and LnIII UIV-sulfate compounds described here are representative of a larger family that will be subsequently reported. As represented here, this family features U84, a ‘superatom’ that organizes into superlattices with both heteroatom monomers and the U6 unit of U84. Superlattices assembled with small LnIII include tetrahedral (interpenetrating), body-centered cubic and cubic-closest packed networks of U84. The body-centered U84 network-type mirrors U6 networks with large LnIII. U84, comprised of 14 linked U6, mirrors the arrangement of the UIV-monomers and sulfate bridges in U6; and, thus, superlattices of U84 can also be described as fractals with three generations. Because the closest UIV-Ln or UIV-TM connectivity is via a sulfate bridge in the reported compounds, there is no magnetic exchange or ordering. One future goal is to minimize or replace the sulfate in our syntheses, and also promote isolation of UV-containing analogues to access targeted magnetic synthons. The U70 ring is a MIV (M=Zr/Hf/An) cluster genre that has never been observed, and also displays unique non-aqueous solubility and differing supramolecular assembly via TMII-counterion linking. We will also access new superlattices of U84 and U70 from organic media, driving assembly from organic capping groups, as well as polyvalent counterion-linking. Methods After discovering the initial crystalline forms, the syntheses with Ln were adjusted and optimized for yield and purity. In the optimized experiments, we combined mixtures of the oxides and chloride salts of the various lanthanides (see methods sections). Optimized syntheses are summarized here, details are provided in the SI, along with procedures for single-crystal X-ray diffraction, magnetic measurements, and SAXS, IR vibration spectroscopy, and TGA.

U(SO4)2, the reactant for all subsequent syntheses, is prepared from 5.0 g of uranyl(VI) acetate in 75 mL of anhydrous ethanol plus 25 mL of concentrated sulfuric acid. This solution is placed under UV light (390-400 nm, 15 W) for 24-48 hours to obtain a green/purple UIV sulfate powder. The solid is collected by vacuum filtration and washing with four 50 mL aliquots of ethanol. (yield = 95.5%) The Ln-UIV (U6 and U84) compounds were all synthesized by similar methods, described generally here with details in the SI. U(SO4)2 (100 mg, 0.23 mmol) is dissolved in 500 µL of 0.5 M H2SO4 in a 2 mL vial. The Ln is introduced as optimized mixtures of Ln2O3 plus LnCl3. The vial is then placed in a sand bath and heated in an oven at 75 ˚C for 24 h. Crystalized products are then filtered out and washed with water followed by 0.5 M HCl to remove any soluble byproduct or starting material. The TM-UIV compounds (U70) were synthesized as follows (details in SI). 100mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of H2O in a 2 mL vial. TMII (Zn, Mn) acetate was added and the vial is then placed in a sand bath and heated in an oven at 75 ˚C for 24 h. Acknowledgements The work performed at OSU (MN and IC) is supported by the Department of Energy, National Nuclear Security Administration (NNSA) under Award Number DE-NA0003763. We acknowledge the Murdock Charitable Trust (Grant No. SR-2017297) for acquisition of thesingle-crystal X-ray diffractometer. The work performed at UofSC (GM and HCzL) was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award No. DE-SC0016574 (Center for Hierarchical Waste Form Materials). Author Contributions IC and MN conceived the experiments, analyzed the data and wrote the paper. IC carried out all experiments except magnetic measurements. GM and HZL provided the magnetic measurements, data interpretation and written contribution to the manuscript. Competing interests The authors declare no competing interests Additional information Supplementary information is available for this paper at …. References 1. Wang L, Liu R, Gu JL, Song B, Wang H, Jiang X, et al. Self-Assembly of Supramolecular Fractals from

Generation 1 to 5. J Am Chem Soc 2018, 140(43): 14087-14096.

2. Yang HB, Northrop BH, Zheng YR, Ghosh K, Stang PJ. Facile Self-Assembly of Neutral Dendritic

Metallocycles via Oxygen-to-Platinum Coordination. J Org Chem 2009, 74(18): 7067-7074.

3. Caminade AM, Yan DY, Smith DK. Dendrimers and hyperbranched polymers. Chem Soc Rev 2015,

44(12): 3870-3873.

4. Newkome GR, Yao ZQ, Baker GR, Gupta VK. Micelles .1. Cascade Molecules - a New Approach to

Micelles - a [27]-Arborol. J Org Chem 1985, 50(11): 2003-2004.

5. Tomalia DA, Naylor AM, Goddard WA. Starburst Dendrimers - Molecular-Level Control of Size,

Shape, Surface-Chemistry, Topology, and Flexibility from Atoms to Macroscopic Matter. Angew Chem Int Edit 1990, 29(2): 138-175.

6. Golub E, Subramanian RH, Esselborn J, Alberstein RG, Bailey JB, Chiong JA, et al. Constructing

protein polyhedra via orthogonal chemical interactions. Nature 2020.

7. Peng Q, Dong YJ, Deng ZX, Li YD. Selective synthesis and characterization of CdSe nanorods and

fractal nanocrystals. Inorg Chem 2002, 41(20): 5249-5254.

8. Shahzad A, Bhang SH, Jung E, Kim WS, Yu T. Hierarchically structured 2D silver sheets with fractal

network. J Materiomics 2018, 4(2): 121-128.

9. Rosseinsky MJ. Fullerene Intercalation Chemistry. J Mater Chem 1995, 5(10): 1497-1513.

10. Claridge SA, Castleman AW, Khanna SN, Murray CB, Sen A, Weiss PS. Cluster-Assembled Materials.

Acs Nano 2009, 3(2): 244-255.

11. Liu C, Sun ZM. Recent advances in structural chemistry of Group 14 Zintl ions. Coordin Chem Rev

2019, 382: 32-56.

12. Mandal S, Reber AC, Qian M, Liu R, Saavedra HM, Sen S, et al. Synthesis, structure and band gap

energy of covalently linked cluster-assembled materials. Dalton T 2012, 41(40): 12365-12377.

13. Qian MC, Reber AC, Ugrinov A, Chaki NK, Mandal S, Saavedra HM, et al. Cluster-Assembled

Materials: Toward Nanomaterials with Precise Control over Properties. Acs Nano 2010, 4(1): 235-240.

14. Cavka JH, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S, et al. A new zirconium inorganic

building brick forming metal organic frameworks with exceptional stability. J Am Chem Soc 2008, 130(42): 13850-13851.

15. Shepelev YF, Smolin YI, Ershov AS, Rademaher O, Sheller G. Determination of the Crystal-Structure of Sodiumtetramethylammonium Silicate Na.7[N(Ch3)4][Si8o20].54h2o at -120-Degrees-C. Kristallografiya+ 1987, 32(6): 1399-1403.

16. Smolin II, Shepelev IF, Ershov AS, Hoebbel D. Isolated Aluminosilicate Radical [Si4al4o12(Oh)8] in

the Tetramethylammonium Aluminosilicate Crystal. Dokl Akad Nauk Sssr+ 1987, 297(6): 1377-1380.

17. Fedeyko JM, Vlachos DG, Lobo RF. Formation and structure of self-assembled silica nanoparticles

in basic solutions of organic and inorganic cations. Langmuir 2005, 21(11): 5197-5206.

18. Mollick S, Fajal S, Mukherjee S, Ghosh SK. Stabilizing Metal-Organic Polyhedra (MOP): Issues and

Strategies. Chem-Asian J 2019, 14(18): 3096-3108.

19. Vardhan H, Yusubov M, Verpoort F. Self-assembled metal-organic polyhedra: An overview of

various applications. Coordin Chem Rev 2016, 306: 171-194.

20. Kalaji A, Soderholm L. Aqueous Hafnium Sulfate Chemistry: Structures of Crystalline Precipitates.

Inorg Chem 2014, 53(20): 11252-11260.

21. Knope KE, Vasiliu M, Dixon DA, Soderholm L. Thorium(IV)-Selenate Clusters Containing an

Octanuclear Th(IV) Hydroxide/Oxide Core. Inorg Chem 2012, 51(7): 4239-4249.

22. Knope KE, Wilson RE, Vasiliu M, Dixon DA, Soderholm L. Thorium(IV) Molecular Clusters with a

Hexanuclear Th Core. Inorg Chem 2011, 50(19): 9696-9704.

23. Falaise C, Kozma K, Nyman M. Thorium Oxo-Clusters as Building Blocks for Open Frameworks.

Chem-Eur J 2018, 24(53): 14226-14232.

24. Yue Z, Guo X, Feng ML, Lin YJ, Ju Y, Lin X, et al. Unexpected Roles of Alkali-Metal Cations in the

Assembly of Low-Valent Uranium Sulfate Molecular Complexes. Inorg Chem 2020.

25. Lin J, Jin GB, Soderholm L. Th-3[Th-6(OH)(4)O-4(H2O)(6)](SO4)(12)(H2O)(13): A Self-Assembled

Microporous Open-Framework Thorium Sulfate. Inorg Chem 2016, 55(20): 10098-10101.

26. Falaise C, Charles JS, Volkringer C, Loiseau T. Thorium Terephthalates Coordination Polymers

Synthesized in Solvothermal DMF/H2O System. Inorg Chem 2015, 54(5): 2235-2242.

27. Loiseau T, Mihalcea I, Henry N, Volkringer C. The crystal chemistry of uranium carboxylates.

Coordin Chem Rev 2014, 266: 69-109.

28. Ejegbavwo OA, Martin CR, Olorunfemi OA, Leith GA, Ly RT, Rice AM, et al. Thermodynamics and

Electronic Properties of Heterometallic Multinuclear Actinide-Containing Metal-Organic Frameworks with "Structural Memory". J Am Chem Soc 2019, 141(29): 11628-11640.

29. Martin NP, Marz J, Feuchter H, Duval S, Roussel P, Henry N, et al. Synthesis and structural

characterization of the first neptunium based metal-organic frameworks incorporating {Np6O8} hexanuclear clusters. Chem Commun 2018, 54(51): 6979-6982.

30. Biswas B, Mougel V, Pecaut J, Mazzanti M. Base-Driven Assembly of Large Uranium Oxo/Hydroxo

Clusters. Angew Chem Int Edit 2011, 50(25): 5744-5747.

31. Dufaye M, Martin NP, Duval S, Volkringer C, Ikeda-Ohno A, Loiseau T. Time-controlled synthesis

of the 3D coordination polymer U(1,2,3-Hbtc)(2) followed by the formation of molecular poly-oxo cluster {U-14} containing hemimellitate uranium(iv). Rsc Adv 2019, 9(40): 22795-22804.

32. Falaise C, Volkringer C, Vigier JF, Beaurain A, Roussel P, Rabu P, et al. Isolation of the Large

{Actinide}(38) Poly-oxo Cluster with Uranium. J Am Chem Soc 2013, 135(42): 15678-15681.

33. Martin NP, Volkringer C, Henry N, Trivelli X, Stoclet G, Ikeda-Ohno A, et al. Formation of a new

type of uranium(iv) poly-oxo cluster {U-38} based on a controlled release of water via esterification reaction. Chem Sci 2018, 9(22): 5021-5032.

34. Sigmon GE, Hixon AE. Extension of the Plutonium Oxide Nanocluster Family to Include {Pu-16} and

{Pu-22}. Chem-Eur J 2019, 25(10): 2463-2466.

35. Soderholm L, Almond PM, Skanthakumar S, Wilson RE, Burns PC. The structure of the plutonium

oxide nanocluster [Pu38O56Cl54(H2O)(8)](14-). Angew Chem Int Edit 2008, 47(2): 298-302.

36. Martin NP, Volkringer C, Roussel P, Marz J, Hennig C, Loiseau T, et al. {Np-38} clusters: the missing

link in the largest poly-oxo cluster series of tetravalent actinides. Chem Commun 2018, 54(72): 10060-10063.

37. Novikov AP, Kalmykov SN, Utsunomiya S, Ewing RC, Horreard F, Merkulov A, et al. Colloid

transport of plutonium in the far-field of the Mayak Production Association, Russia. Science 2006, 314(5799): 638-641.

38. Suzuki Y, Kelly SD, Kemner KM, Banfield JF. Radionuclide contamination - Nanometre-size

products of uranium bioreduction. Nature 2002, 419(6903): 134-134.

39. Misra A, Kozma K, Streb C, Nyman M. Beyond Charge Balance: Counter-Cations in Polyoxometalate Chemistry. Angew Chem Int Edit 2020, 132(2): 596-612.

40. Knope KE, Soderholm L. Solution and Solid-State Structural Chemistry of Actinide Hydrates and

Their Hydrolysis and Condensation Products. Chem Rev 2013, 113(2): 944-994.

41. Lundgren G. The Crystal Structure of U6O4(OH)4(SO4)6. Ark Kemi 1953, 5: 349– 363.

42. Loble MW, Keith JM, Altman AB, Stieber SCE, Batista ER, Boland KS, et al. Covalency in

Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl(6)(x-) (x=3, 2). J Am Chem Soc 2015, 137(7): 2506-2523.

43. Frank P, Szilagyi RK, Gramlich V, Hsu HF, Hedman B, Hodgson KO. Spin-Polarization-Induced

Preedge Transitions in the Sulfur K-Edge XAS Spectra of Open-Shell Transition-Metal Sulfates: Spectroscopic Validation of sigma-Bond Electron Transfer. Inorg Chem 2017, 56(3): 1080-1093.

44. Shevchenko EV, Talapin DV, Murray CB, O'Brien S. Structural characterization of self-assembled

multifunctional binary nanoparticle superlattices. J Am Chem Soc 2006, 128(11): 3620-3637.

45. Chen Z, O'Brien S. Structure direction of II-VI semiconductor quantum dot binary nanoparticle

superlattices by tuning radius ratio. Acs Nano 2008, 2(6): 1219-1229.

46. Sessoli R, Powell AK. Strategies towards single molecule magnets based on lanthanide ions.

Coordin Chem Rev 2009, 253(19-20): 2328-2341.

47. Vanagas NA, Wacker JN, Rom CL, Glass EN, Colliard I, Qiao YS, et al. Solution and Solid State

Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates. Inorg Chem 2018, 57(12): 7259-7269.

48. Knope KE, Vanagas NA, Higgins RF, Wacker JN, Romar D, Asuigui C, et al. Mononuclear to

Polynuclear U(IV) Structural Units: Effects of Reaction Conditions on U‐Furoate Phase Formation. Chem-Eur J 2020.

49. Usman M, Morrison G, Klepov VV, Smith MD, zur Loye HC. Flux crystal growth, structure, magnetic

and optical properties of a family of alkali uranium(IV) phosphates. J Solid State Chem 2019, 270: 19-26.

50. Morrison G, Ramanantoanina H, Urland W, Smith MD, zur Loyet HC. Flux Synthesis, Structure,

Properties, and Theoretical Magnetic Study of Uranium(IV)-Containing A(2)USi(6)O(15) (A = K, Rb) with an Intriguing Green-to-Purple, Crystal-to-Crystal Structural Transition in the K Analogue. Inorg Chem 2015, 54(11): 5504-5511.

51. Klepov VV, Pace KA, Calder S, Felder JB, zur Loye HC. 3d-Metal Induced Magnetic Ordering on

U(IV) Atoms as a Route toward U(IV) Magnetic Materials. J Am Chem Soc 2019, 141(9): 3838-3842.

52. Kindra DR, Evans WJ. Magnetic Susceptibility of Uranium Complexes. Chem Rev 2014, 114(18):

8865-8882.

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Supplemental Information for Supramolecular Assembly of U(IV) Clusters and Superatoms Ian Colliard,1 Gregory Morrison,2 Hans-Conrad zur Loye2 and May Nyman1*

1Department of Chemistry, Oregon State University, Corvallis, OR 97331, USA 2Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA *correspondence: [email protected] Outline

1) Experimental Section pg. 2 2) Crystallographic Studies pg. 4 3) Notes on Crystal Structures, Refinement, and Modeling of Disorder pg. 4

a. La-U6; crystallographic table, notes, figures pg. 5 b. Y-U84; crystallographic table, notes, figures pg. 7 c. ErU6-(U84)2; crystallographic table, notes, figures pg. 10 d. LuU-U84; crystallographic table, notes, figures pg. 14 e. Mn-U70; crystallographic table, notes, figures pg. 17 f. Mn-(U6U70)2; crystallographic table, notes, figures pg. 20 g. Zn-U70; crystallographic table, notes, figures pg. 24

4) Summary of Bond Lengths pg. 26 5) Summary of Solvent Accessible Void Masks pg. 26 6) Bond Valence Calculations pg. 27 7) Magnetic Susceptibility pg. 29 8) Small Angle X-ray Scattering pg. 32 9) IR Spectroscopy pg. 34 10) Thermogravimetric Analysis pg. 35

mailto:[email protected]

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Experimental section: Caution! U238 is an alpha-emitting radioisotope. Standard precautions should be followed when handling radioactive materials. Materials: UO2(CH3COO)2 , concentrated H2SO4 (98% Macron Fine Chemicals), La2O3 (99.99% Alfa Aesar ?), LaCl3.7H2O (99.99%, Alfa Aesar), Y2O3 (99.9%, Alfa Aesar), YCl3.7H2O (99.9, Alfa Aesar), Er2O3 (99.9% Johnson Matthey Electronics), ErCl3.6H2O (99.9%, Alfa Aesar), Lu2O3 (99.9%, Sigma Aldrich), LuCl3.6H2O (99.9%, Sigma Aldrich), Mn(CH3COO)2.4H2O (99.0%, Sigma Aldrich), Zn(CH3COO)2.2H2O (99.0%, Sigma Aldrich), Tetrabutylammonium Chloride (>97%, Sigma Aldrich) were all used as received. Millipore-filtered water with a resistance of 18.2 MΩ•cm was used in all reactions. Synthesis of U(SO4)2: 5.0 g of uranyl acetate is dissolved in 75 mL of anhydrous ethanol. 25 mL of concentrated sulfuric acid is added dropwise. After complete dissolution of the uranyl acetate, the solution is placed under UV light (390-400 nm, 15 W) for 24-48 hours. The uranium is reduced and precipitates as uranium sulfate. The green/purple powder is vacuum filtered and washed with four 50 mL aliquots of ethanol. The powder is then stored in a desiccator. Percent yield is 95.5% LnIII-UIV-sulfate phases. Synthesis of La4U6(OH)4(O)4(SO4)12(H2O)24.5 •20H2O, (La-U6): 100 mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of 0.5 M H2SO4 in a 2 mL vial. To the solution, 35 mg of La2O3 (0.107 mmol) and 35 mg of LaCl3.7H2O (0.094 mmol) is added. The vial is then placed in a sand bath and heated in an oven at 75 ̊ C for 24 h. During the hydrothermal process, crystals of U6-La appear. The crystals are then filtered and washed with 2 mL of water, followed by 2 mL of 0.5 M HCl to remove any soluble material. Yield is 93.0% based of U. Synthesis of Y16(U6(OH)4(O)4)14(SO4)108(H2O)126.5•156(H2O), (Y-U84): 100 mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of 0.5M H2SO4 in a 2 mL vial. To the solution, 35 mg of Y2O3 (1.55 mmol) and 35 mg of YCl3.7H2O (0.108 mmol) is added. The vial is then placed in a sand bath and heated in an oven at 75 ˚C for 24 h. During the hydrothermal process, crystals of U84-Y appear. The crystals are then filtered out and washed with 2 mL of water, followed by 2 mL of 0.5 M HCl to remove any soluble material. Yield is 84.4% based of U. Synthesis of U6(OH)4(O)4(H2O)12(Er16(U6(OH)4(O)4)14(SO4)111(H2O)130)2•366.5H2O, (ErU6-(U84)2): 100 mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of 0.5 M H2SO4 in a 2 mL vial. To the solution, 35 mg of Er2O3 (0.091 mmol) and 70 mg of ErCl3.6H2O (0.183 mmol) is added. The vial is then placed in a sand bath and heated in an oven at 75 ˚C for 24 h. During the hydrothermal treatment, crystals of Er-U84 (will be reported in a later publication) and ErU6-(U84)2 co-

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crystallize. The crystals are then filtered out and washed with 2 mL of water, followed by 2 mL of 0.5 M HCl to remove any soluble material. Percent yields could not be determined due to the presence of co-crystallites. Synthesis of U4Lu12(U6(OH)4(O)4)14(SO4)110(H2O)116 •324H2O, (LuU-U84): 100 mg of U(SO4)2

(0.23 mmol) is dissolved in 500 µL of 0.5 M H2SO4 in a 2 mL vial. To the solution, 35 mg of Lu2O3 (0.088 mmol) and 120 mg of LuCl3.6H2O (0.308 mmol) is added. The vial is then placed in a sand bath and heated in an oven at 75 ˚C for 24 h. During the hydrothermal process, crystals of Lu-U84, LuU6-(U84)2, and LuU-U84 co-crystalize. The crystals are then filtered out and washed with 2 mL of water, followed by 2 mL of 0.5 M HCl to remove any soluble material. Lu-U84 and LuU6-(U84)2 will be reported in a later publication. Percent yields could not be determined due to the presence of co-crystallites. TMII-UIV-sulfate phases. Synthesis of Mn4(H2O)16[(U6(OH)4(O)4)(H2O)9)(U70(OH)34(O)66(SO4)65(H2O)61]2•549.4H2O, (Mn-(U6U70)2): 100 mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of H2O in a 2 mL vial. To the solution, 50 mg of Mn(II) acetate (0.204 mmol) is added. The vial is then placed in a sand bath and heated in an oven at 75 ̊ C for 48 h. During the hydrothermal process, crystals of Mn-(U6U70)2,

Mn-U70 can also co-crystallize. The crystals are then filtered out and washed with 2 mL of water. Percent yield of 13.4%. Synthesis of Mn6U70(OH)36(O)64(SO4)64(H2O)44•363H2O, (Mn-U70): 100 mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of H2O in a 2 mL vial. To the solution, 50 mg of Mn(II) acetate (0.204 mmol) is added. Additionally, 100 μL of 1 g/mL TBACl solution in H2O is added. The vial is then placed in a sand bath and heated in an oven at 75 ˚C for 24 h. During the hydrothermal process, crystals of Mn-U70 grow. The crystals are then filtered out and washed with 2 mL of water. Percent yield 76.4%. Synthesis of (Zn(H2O)6)3.5Zn2.5U70(OH)36(O)64(SO4)64(H2O)54.5•145H2O, (Zn-U70): 100mg of U(SO4)2 (0.23 mmol) is dissolved in 500 µL of H2O in a 2 mL vial. To the solution, 50 mg of Zn(II) acetate (0.204 mmol) is added. Additionally, 200 μL of 1 g/mL TBACl solution in H2O is added. The vial is then placed in a sand bath and heated in an oven at 75 ˚C for 3-4 days. During the hydrothermal process, crystals of Zn-U70 grow. The crystals are then filtered out and washed with 2 mL of water. Percent yield 70.6%.

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Crystallographic Studies: The La-U6 (CSD 1982467) crystals were collected on a Bruker DUO-APEX II CCD area detector at 173 K using Cu radiation (λ=1.54178 Å). Data reduction was accomplished using SAINT V8.34a. Y-U84 (CSD 1982469), ErU6-(U84)2 (CSD 1982470), LuU-U84 (CSD 1982594), Mn-U70 (CSD 1982472), Zn-U70 (CSD 1982479), were collected at 173 K on a Rigaku Oxford SynergyS equipped with a PhotonJet S Cu source (λ=1.54178 Å) and hyPix-6000HE photon counting detector. All images were collected and processed using CrysAlisPro Version 171.40_64.53 (Rigaku Oxford Diffraction, 2018) (1). After integration both (Analytical) absorption and empirical absorption (spherical harmonic, image scaling, detector scaling) corrections were applied (2). Mn-(U6U70)2 (CSD 1982618) was collected at 100 K on a Rigaku Oxford SynergyS equipped with a PhotonJet S Mo source (λ=0.71073 Å) and hyPix-6000HE photon counting detector. All images were collected and processed using CrysAlisPro Version 171.40_64.53 (Rigaku Oxford Diffraction, 2018) (1). After integration both (Analytical) absorption and empirical absorption (spherical harmonic, image scaling, detector scaling) corrections were applied (2). All eight structures were solved by Intrinsic Phasing method from SHELXT program (3), developed by successive difference Fourier syntheses, and refined by full-matrix least square on all F2 data using SHELX (4) via OLEX2 interface (5). Notes on Crystal Structures, Refinement, and Modeling of Disorder:

All seven of the structures exhibit some disorder, either site-occupancy or positional disorder. As such, we can summarize four main types of disorder encountered with the reported structures. The first is solvent disorder, please refer to the section on Solvent Accessible Void Mask. Second, is positional and site occupancy disorder of sulfates: this type is mostly encounter with the structures that feature the U84 unit, as some of sulfates located on the periphery are loosely bound. The next type of disorder is site-occupancy of lanthanide or transition metal monomers. The last type of disorder can be described as positional disorder of major structural units: this is encountered in two structures, where there is a positional disorder of entire hexameric units, more information on the specific examples below. Modeling of the disorder for all seven reported structures was carried using the same methodology. For the solvent disorder, solvent mask was used, please see Summary of Solvent Accessible Void Mask section. For the disordered sulfate, each sulfur atom was refined with a ‘free’ occupancy, and after several refinement cycles, the occupancy factor for each was left to converge and then rounded up to the nearest fourth, in some instances to the nearest third or fifth. The same was applied for the lanthanide or transition metal monomers. We first refined the monomers with ‘free’ occupancy. After several refinement cycles, the occupancy factor for each monomer was left to converge and then rounded up to the nearest fourth, in some instances to the nearest third. Before finalizing the occupancy of a monomer or of a sulfate, the resulting thermal parameters from anisotropic refinements were compared with the rest of the structure, to ensure comparable

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numbers. Additionally, any resulting formula was checked and adjusted, if necessary, for charge balance. Below is more detailed descriptions of the local and long range structure for each sample, additionally commenting on any particular disorder and modeling. La-U6, La4U6(OH)4(O)4(SO4)12(H2O)24.5 •20H2O, crystallizes in the monoclinic space group P21/a. The U(IV) hexamer is the typical core [U6(OH)4(O)4)]12+. Summary of the bond distances can be found on Table SI-8. Each hexamer can be described as sitting in the center of a distorted cube with the six U-polyhedra of U6 occupying the six cube faces, and eight La located on the cube corners (La-La distances 6.6543(6)-9.1407(8) Å along a cube edge). Then these cubes are linked by the La-corners; each La joins two clusters into a 3-dimensional checkerboard arrangement. Since the linkage is via corners, the structure exhibits large voids along the b-axis that run the length of the crystal. Solvent mask was used to describe the voids, see Table SI-9. This phase features disorder in the water molecules coordinated to the lanthanum monomers. The disorder was modeled by splitting the occupancy of the coordinating water ligands. Additionally, the typical core [U6(OH)4(O)4)]12+ features the O/OH disorder on the μ3-oxygens, see figure SI-1.

Figure SI-1. Oxo/hydroxo disorder of the uranium hexamer core, U in green, oxo in orange, hydroxo in red.

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Table-SI-1. Crystallographic Data

Identification code La-U6 Empirical formula La8O172S24U12

Formula weight 7489.08 Temperature/K 173 Crystal system monoclinic Space group P21/a

a/Å 22.2411(8) b/Å 17.3434(7) c/Å 22.9339(9) α/° 90 β/° 108.0838(15) γ/° 90

Volume/Å3 8409.5(6) Z 2

ρcalcg/cm3 2.951 μ/mm-1 54.002 F(000) 6624

Crystal size/mm3 0.065 × 0.046 × 0.012 Radiation CuKα (λ = 1.54184 Å)

2Θ range for data collection/° 4.068 to 134.606 Index ranges -26 ≤ h ≤ 26, -20 ≤ k ≤ 20, -27 ≤ l ≤ 27

Reflections collected 69086 Independent reflections 14886 [Rint = 0.0624, Rsigma = 0.0469]

Data/restraints/parameters 14886/0/1055 Goodness-of-fit on F2 1.043

Final R indexes [I>=2σ (I)] R1 = 0.0348, wR2 = 0.0840 Final R indexes [all data] R1 = 0.0414, wR2 = 0.0871

Largest diff. peak/hole / e Å-3 2.09/-1.45

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Y-U84, Y16(U6(OH)4(O)4)14(SO4)108(H2O)126.5•156H2O. Here we describe the disorder of the Y3+-monomers. Disordered yttrium monomers decorate the surface of the U84 cluster and link the U84 cluster to other U84 clusters, making an extended framework. The framework builds up from each U84 linked to eight others via bridging yttrium monomers, four above and four bellow. The bridging monomers are fully occupied with three coordinating monodentate sulfates in a square anti-prismatic. Two of the coordinating sulfates bridge U6f and U6c. The 3rd sulfate is of the neighboring U84 cluster, more specifically the sulfate on the periphery of the U6c, which don’t participate in bridging between the hexamers. There are four disordered (over two positions each) Y3+ bound to each U6f, and four additional partially occupied Y3+ bound to each U6c. Each Y3+ is 7-8 coordinate, bound to sulfates from U84aand water molecules. The bridging, and ‘fully’ Y3+ are coordinated by three sulfates, whereas the disordered (by site occupancy) are two to one sulfate-coordinated. The structure features positional and site occupancy disorder on the Y3+-monomers, the sulfate, and coordinating waters. The modeling of the disordered was handled as described above. A summary of the bond distances can be found on Table SI-8, and a summary of the solvent mask in Table SI-9. Table SI-2. Crystallographic Data

Identification code Y-U84 Empirical formula O1345S216U168Y32

Formula weight 71279.12 Temperature/K 173 Crystal system tetragonal

Space group P4/m a/Å 29.8346(2) b/Å 29.8346(2) c/Å 44.5195(4) α/° 90 β/° 90 γ/° 90

Volume/Å3 39627.0(6) Z 1

ρcalcg/cm3 2.987 μ/mm-1 52.701 F(000) 30920







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Figure SI-2 a) Polyhedral representation of [U6(O)4(OH)4(SO4)12]12-, corner U6c. b) Polyhedral representation of [U6(O)4(OH)4(SO4)16]20-

, face U6f. c) Polyhedral representation of the connectivity between two U84, via Y-monomers, in grey. d) Polyhedral representation of U84 with fully occupied Y monomers, in grey, that will bridge to neighboring U84’s. e) Polyhedral representation of U84 with all Y monomers, in grey, decorating the entire U84

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U6-(ErU84)2, U6(OH)4(O)4(H2O)12(Er16(U6(OH)4(O)4)14(SO4)111(H2O)130)2•366.5H2O. This structure shares the same U84 parent cluster as described above, the disorder on the sulfates was handled as described above.

This structure features a positional disorder of the U6tet, which is located in a void of tetrahedral symmetry. The hexamer is thus described by two uranium centers localized on a special position (Wyckoff 24h) with an occupancy of 0.25. This resulted in the hexamer being disordered over four position, eight when including the symmetrically equivalent position. The unique position of the hexamers can be resolved by limiting the U-U distances between 3.740 Å – 3.920 Å, followed by color-coding each different position, see figure SI-3b. The U6 is positioned so that a face or edge of the hexamer coordinates to the U84, where the peripheral sulfates of U6c within a neighboring U84 cluster can bridge to it, see figure SI-3c & d. Additionally, the bridging sulfates between the U84 and the hexamer are disordered in two positions to accommodate the different positions of the U6, see figure SI-3c and SI-3d. During the refinement process, the bridging oxo & hydroxo groups in this disordered hexamer were unable to be located due to the superposition of the U to the O created by the disorder.

Fully occupied ErIII monomers link the face of the U84 to the adjacent in the tetrahedron. As aforementioned there are two interpenetrating networks, both networks are bridged and interconnected by Er-disordered monomers via the remaining corners and faces of the U84. However, the fully occupied Er monomers are 9-fold coordinate with four from the sulfates and the remaining five are coordinating waters in a capped square antiprism geometry. Two of the sulfates are on the periphery of the U6f in the U84 cluster and the other two sulfates are of the neighboring U84 cluster, fig. SI-3e. A summary of the bond distance and solvent mask results are in table SI-8 & 9, respectively.

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Table SI-3. Crystallographic Data Identification code ErU6-(U84)2 Empirical formula Er63.99O2813.77S443.96U347.97

Formula weight 152785.5 Temperature/K 173 Crystal system cubic

Space group Pn-3 a/Å 43.94950(10) b/Å 43.94950(10) c/Å 43.94950(10) α/° 90 β/° 90 γ/° 90

Volume/Å3 84891.0(6) Z 1.00008

ρcalcg/cm3 2.989 μ/mm-1 52.287 F(000) 65984

Crystal size/mm3 0.096 × 0.082 × 0.078 Radiation CuKα (λ = 1.54184)






12

Figure SI-3. a) Ball and stick representation of four U84’s in a tetrahedron, with the disordered hexamer in the middle, bridging Er monomers in black. b) Color-coding the disordered U6, each color represents one possible position for each U atom in a hexamer. c) Polyhedral representation of the U84 cluster with the disordered U6 coordinating via an ‘edge’. d) Polyhedral representation of the U84 cluster with the disordered U6 coordinating via a ‘face’ e) Polyhedral representation of the fully occupied Er-monomer (in grey) connectivity to the U84 cluster via face U6. f) Ball and stick representation of the connectivity between the two interpenetrating networks. Fully occupied Er (in black), disordered Er in light grey link the blue network to the green.

13

LuU-U84, U4Lu12(U6(OH)4(O)4)14(SO4)110(H2O)116 •324H2O. This structure shares the same U84 parent cluster as described above, the disorder on the sulfates was handled as described above.

The framework can be also described as chains of the U84 clusters linked together by uranium monomers. The chains of the U84 are also linked to each other by uranium and lutetium monomers. Viewing along the c-axis, or down the chains, the U84 clusters eclipse each other, only coordinating to two U84’s. Perpendicular to the c-axis, or parallel to the ab plane, six U84 clusters are surrounding a single U84; where three U84 are slightly above the plane and three slightly below the plane, see figures. The U monomers are eight-coordinate with six bonds linking the sulfates (three from each adjacent U84), and two from (positionally disordered) coordinating waters, see figure SI-4b. The UIV-monomer bridging U84 units along the c-axis sits just off a special position (C3 rotation axis), so it is disordered over three positions, each 33% occupied, see figure SI-4e. A distance restrain was placed on one of the oxygens on the disordered sulfate that bridges to the disordered U-monomer. Fully occupied lutetium monomers, bridge instead from the U6f, being eight-coordinate, with four coordinating waters, see figure SI-4c. As with the previous structures, disordered lutetium monomers also decorate the U84. A summary of the bond distances can be found in Table SI-8, and a summary of the solvent mask in Table SI-9.

14

Table SI-4. Crystallographic Data Identification code LuU-U84 Empirical formula Lu72O4092S660U528

Formula weight 224909.28 Temperature/K 172.99(10) Crystal system trigonal

Space group R-3c a/Å 48.84142(13) b/Å 48.84142(13) c/Å 66.7088(2) α/° 90 β/° 90 γ/° 120

Volume/Å3 137813.0(8) Z 1

ρcalcg/cm3 2.71 μ/mm-1 48.544 F(000) 96984







15

Figure SI-4. a) Ball and stick representation U84’s with bridging U-monomers in light green, view along c. b) Polyhedral representation of the U-monomer connectivity to the U84 cluster via face U6. c) Polyhedral representation of the Lu-monomer (in grey) connectivity to the U84 cluster via corner U6. d) Ball and stick representation of the U-monomer just off the special position along the c-axis e) Polyhedral representation of extended framework, U in green, sulfate in yellow.

16

Mn-U70, Mn6U70(OH)36(O)64(SO4)64(H2O)44•360H2O.

The manganese analog of the U70 structure, features disordered Mn monomers, both bridge the chain of U70 to neighboring chains, creating a 3D-framework; but also help to bridge U70-to- U70 with in the chain, see figure SI-7d. The disorder of the monomers was handled as described above. All Mn monomers are six coordinates, with four coordinating waters. A summary of bond distances and solvent mask results are in table SI-8 and SI-9, respectively. Bond Valence Sum calculations were performed on the bridging oxygens in order to determine the charge of the ring. Based on the BVS calculations, in Table SI-10, and the number of counterions, it was determined that the U70 ring exhibit O/OH disordered, as is common with the U-hexamer; the disorder is suspected to primarily reside on the μ4-Ο.

Table SI-5. Crystallographic Data

Identification code Mn-U70 Empirical formula Mn3O213.5S32U35

Formula weight 12937.79 Temperature/K 173 Crystal system triclinic

Space group P-1 a/Å 17.90832(6) b/Å 29.14308(10) c/Å 33.54864(9) α/° 103.1396(3) β/° 97.8685(3) γ/° 101.9521(3)

Volume/Å3 16367.11(10) Z 2

ρcalcg/cm3 2.625 μ/mm-1 51.539 F(000) 11030







17

Figures SI-5. a) Ball and stick representation of the [U70O100] core (sulfurs and oxygens of sulfates not shown). b) Polyhedral representation of the U70 ring with Mn monomers, in purple, decorating the ring. c) Polyhedral representation of bridging Mn-monomer, in purple. d) Polyhedral representation of the stacking of the U70 ring.

18

Mn-(U6U70)2, Mn4(H2O)16[(U6(OH)4(O)4)(H2O)9)(U70(OH)34(O)66(SO4)65(H2O)61]2•549.4H2O, The compound has a similar parent U70 ring structure, [U70(OH)34(O)66]+114. U4+-O/OH bonds in U70 are typical, the charge of the U70 ring was determined by BVS, as above, see Table SI-10. As with the previous structure, sulfates link the rings into staggered chains. In this case, there is a chain of sandwich structures creating a framework; made by two U70 rings sandwiching two uranium hexamers (figure 4b). As with the previous structure, manganese monomers serve to link the chain of rings to each other and in the stacking of the sandwich rings, very similar to the Mn-U70 structure. A summary of the bond distances can be found in Table SI-8, and a summary of the solvent mask in Table SI-9. Disorder on the Mn-monomers and any lattice water was modelled as described above.

This structure features positional disordered U6, similarly as with the ErU6-(U84)2 structure. Modeling of the disordered required data collection using Mo-radiation, the higher resolution made it more suitable to locate all μ3-oxygens, for the disordered hexamers. A data collection of 100 K was also chosen to limit the decay of the crystal itself, minimize thermal vibrations, and limit the loss of solvated water molecules; all of which affect crystallinity. Modeling of the disorder was performed similarly as above. Each individual position of the hexamer had to be refined, as such five pairs of hexamers at 1/5th occupancy were modeled the same way. Due to the high positional disorder, and the accompanying lattice water disorder, several restraints were applied to aid in the modeling of the disorder.

Distance and angle restraints were placed in the μ3-oxygens, within the hexamer, and within the oxygen of the bridging sulfates. Additionally, restraints on the atomic displacement parameters were placed for the U, O, and S, located within the disordered area. By constraining the ADP of those atoms, we were able to constrain the parameters to be more ‘spherical;’ this aided in modeling of the atomic positions accurately. Due to the disorder, refining the ADP of the atoms freely resulted in very prolate shaped atoms; caused by the smearing of electron-density peaks along the disorder.

The outermost μ3-oxygens of the hexamers were refined to be fully occupied, to describe the superposition with solvent waters. Unfortunately, several high residual electronic densities, remained unassigned and could not be modeled. We suspect that these high q-peaks, which are located around 2.4 Å away from the neighboring U center, are coordinating water molecules. Alternatively, the high q-peaks could arise from the superposition of less energetically favorable positions for the hexamers, see figure SI-6d.

19

Table SI-6. Crystallographic Data Identification code Mn-(U6U70)2 Empirical formula Mn4O922.4S130U152

Formula weight 55326.52 Temperature/K 100.0(3) Crystal system triclinic


Volume/Å3 37194.4(6) Z 1

ρcalcg/cm3 2.47 μ/mm-1 16.768 F(000) 23543

Crystal size/mm3 0.187 × 0.112 × 0.072 Radiation MoKα (λ = 0.71073 Å)






22

Figure SI-6 a) Polyhedral representation of the Mn-(U6U70)2, showcasing the disordered hexamer (top view). Each color corresponding to a unique position. b) polyhedral representation of the Mn-(U6U70)2, side view, showing bridging sulfates, in yellow polyhedral, to the U6 c) polyhedral representation of the Mn-(U6U70)2, showcasing the disordered hexamer. Each color corresponding to a unique position. Colors with 50% opacity correspond to potentially additional disorder positions, to account for the high residual q-peaks. d) Screenshot showing one example of the high residual q-peaks (brown sphere) that could not be modelled. Distance between q-peaks (shown, approx. 3.5 Å), to neighboring U (approx. 2.4 Å)

23

Zn-U70, (Zn(H2O)6)3.5Zn2.5U70(OH)36(O)64(SO4)64(H2O)54.5•145H2O. The structure features the U70 core described above. As with the Mn-U70, the zinc analogue features disordered Zn monomers, the structure however is no longer a 3D framework, but instead 1D-network. All Zn monomers are 6-coordinate, with 5-6 coordinating waters. The aqua-Zn monomers bridge and stabilize the chain of U70 via hydrogen bonding. The terminal Zn monomers, with 5 coordinating waters and only one sulfate, similarly bridge U70 to U70 within the chain via hydrogen bonding, see fig. SI-7d. A summary of bond distances and solvent mask results are in Tables SI-8 and SI-9, respectively. Bond Valence Sum calculations were performed on the bridging oxygens in order to determine the charge of the ring (Table SI-10). Table SI-7. Crystallographic Data

Identification code Zn-U70 Empirical formula O437.5S64U70Zn6

Formula weight 26106.16 Temperature/K 293(2) Crystal system triclinic


Volume/Å3 14800.6(4) Z 1

ρcalcg/cm3 2.929 μ/mm-1 56.273 F(000) 11144







24

Figure SI-7.a) Polyhedral representation of the U70 ring with Zn monomers, in grey, decorating the ring. Two types exist, Zn(H2O)6

2+ and sulfate-linked Zn, O3SO-Zn(H2O)52+. b) polyhedral

representation of the interaction between Zn monomers and the neighboring rings. c) Polyhedral representation of the stacking of the U70 ring with terminal Zn monomers in grey, note they do not bridge to the neighboring ring. d) Stacking of the U70 rings, viewed along a.

25

Table SI-8. Summary of Bond distances

Crystal U-O (Å) U-OH (Å) U-OH2 (Å) U-OSO3 (Å) M-OSO3 (Å) M-OH2 (Å) La-U6 2.174(17) -

2.274(16) 2.388(6)-2.52(2)

2.622(15)-2.661(15)

2.363(6)-2.466(7)

2.467(7)-2.569(8)

2.414(17)-2.778(16)

Y-U84 2.170(18) -2.330(4)

2.360(3)-2.66(3)

2.55(3)-2.79(2)

2.338(17)-2.457(13)

2.17(18)-2.53(7)

2.09(8)-2.81(7)

ErU6-(U84)2

2.160(2) -2.33(5)

2.360(2)-2.52(3)

2.631(18)-2.821(18)

2.07(6)-2.569(18)

2.21(2)-2.431(14)

2.08(3)-2.85(5)

LuU-U84 2.176(19) -2.269(8)

2.37(2)-2.64(3)

2.36(4)-2.85(16)

2.279(4)-2.51(17)

2.29(15)-2.49(15)

1.96(5)-2.59(4)

Mn-U70 2.154(10)-2.594(9) 2.381(13)-2.679(11)

2.38(10)-2.734(9)

2.111(12)-2.416(16)

1.766(8)-2.7(4)

Zn-U70 2.149(15)-2.621(19) 2.22(5)-2.71(15)

2.35(2)-2.702(19)

2.04(2)-2.06(2)

1.91(8)-2.25(3)

Mn-(U6U70)2

2.161(13)-2.593(16) 2.2(13)-2.705(13)

2.316(15)-2.739(14)

2.091(18)-2.264(19)

2.06(3)-2.41(3)

Summary of Solvent Accessible Void Masks All of the structures have solvent accessible voids that comprise 15% or greater of the unit cell volume. A solvent mask (6) was applied to every structure, the results of the masks are summarized in Table SI-9. In each case, the electron count was in good agreement with the solvent accessible void volume, assuming 30-40 Å3 per water molecule (6-8). As such the electron count was used to describe the solvent mask. Table SI-9. Summary of Solvent Mask results

Crystal Total Void/U.C.* (Å3)

Void Percent/U.C.

Electron Count/U.C.

Waters/F.U.** (mask)

Waters/F.U. (Refined)

Total Waters

La-U6 1,632.20 19.4 583.2 14.5 5.5 20 Y-U84 10,577.60 26.7 3,089.40 154 2 156 ErU6-(U84)2 25,797.10 30.4 6,870.10 343.5 23 366.5 LuU-U84 52,780.50 38.3 18,608.00 310 14 324 Mn-U70 8,115.10 49.6 3603.1 360 3 363 Zn-U70 6,319.70 42.7 1394.1 139 6 145 Mn-(U6U70)2

17,932.00 48.2 4848.6 485 64.4 549.4

*Unit cell (U.C), **Formula Unit (F.U.)

26

Table SI-10. Bond Valence Sum of Mn-U70 and Zn-U70 Crystal Mn-U70 Crystal Zn-U70 O Atom BVS Designation O Atom BVS Designation

18 1.718 O/OH 21 1.716 O/OH 25 1.735 O/OH 10 1.679 O/OH 54 1.765 O/OH 32 1.752 O/OH 72 1.750 O/OH 59 1.720 O/OH 80 1.733 O/OH 68 1.744 O/OH 12 1.733 O/OH 61 1.708 O/OH

225 1.736 O/OH 148 1.767 O/OH 136 1.744 O/OH 155 1.749 O/OH 229 1.747 O/OH 154 1.743 O/OH 156 1.729 O/OH 19 1.743 O/OH 24 2.124 O 85 2.166 O 46 2.100 O 12 1.934 O 53 2.147 O 11 2.120 O 71 2.092 O 54 2.054 O 92 2.247 O 8 2.226 O

111 2.041 O 4 2.168 O 135 2.163 O 18 2.234 O 224 2.126 O 87 2.125 O 147 2.148 O 6 2.108 O 159 2.121 O 5 2.106 O 23 2.185 O 28 2.140 O 47 2.153 O 35 2.153 O 52 2.204 O 23 2.119 O 70 2.099 O 2 2.123 O 91 2.133 O 86 2.069 O

110 2.079 O 14 2.106 O 126 2.124 O 163 2.025 O 220 2.110 O 145 2.172 O 146 2.184 O 104 2.168 O 160 2.071 O 7 2.172 O 21 1.003 OH 36 2.127 O 51 1.104 OH 3 2.171 O 94 1.068 OH 16 2.087 O

132 1.086 OH 1 2.163 O 158 1.209 OH 22 2.131 O 20 1.082 OH 57 2.006 O 50 1.099 OH 107 2.149 O 95 1.105 OH 84 2.090 O

133 1.049 OH 20 2.136 O 148 1.055 OH 9 2.152 O 19 2.118 O 66 1.028 OH 22 2.123 O 105 1.114 OH 48 2.085 O 78 1.077 OH 62 2.147 O 162 1.171 OH 96 2.141 O 25 1.096 OH 93 2.107 O 169 1.081 OH

125 2.123 O 80 1.086 OH 134 2.105 O 15 1.054 OH 145 2.123 O 111 1.066 OH 157 2.106 O 112 1.049 OH

27

Table SI-11. Bond Valence Sum of Mn-(U6U70) Crystal Mn-(U6U70)2 O Atom BVS Designation O Atom BVS Designation

98 1.741 O/OH 47 2.097 O 8 1.750 O/OH 40 2.146 O

11 1.757 O/OH 37 2.156 O 18 1.746 O/OH 32 2.157 O 20 1.753 O/OH 29 2.101 O 27 1.727 O/OH 22 2.114 O 30 1.719 O/OH 385 2.092 O 35 1.731 O/OH 13 2.121 O 38 1.739 O/OH 10 2.112 O 45 1.761 O/OH 2 2.174 O 48 1.777 O/OH 3 2.154 O 55 1.809 O/OH 7 2.093 O 58 1.736 O/OH 16 2.094 O 65 1.800 O/OH 17 2.171 O 68 1.762 O/OH 23 2.126 O 75 2.035 O/OH 26 2.160 O 80 1.821 O/OH 6 2.083 O 85 1.742 O/OH 379 2.118 O 88 1.796 O/OH 41 2.132 O 95 1.760 O/OH 44 2.127 O 1 2.147 O 51 2.120 O 9 2.025 O 54 1.937 O

12 2.091 O 61 2.121 O 19 2.152 O 64 2.086 O 21 2.136 O 71 2.151 O 28 2.150 O 74 2.122 O 31 2.184 O 78 2.123 O 36 2.128 O 84 2.120 O 39 2.143 O 91 2.097 O 46 2.133 O 94 2.081 O 49 2.110 O 4 1.068 OH 56 2.147 O 5 1.099 OH 59 2.078 O 15 1.069 OH 66 2.100 O 14 1.069 OH 69 2.170 O 25 1.078 OH 76 2.139 O 24 1.056 OH 79 2.196 O 34 1.086 OH 86 2.101 O 33 1.181 OH 89 2.202 O 43 1.061 OH 96 2.157 O 42 1.018 OH 97 2.094 O 53 1.171 OH 90 2.154 O 52 1.126 OH 87 2.097 O 62 1.180 OH 81 2.157 O 63 1.029 OH 77 2.087 O 72 1.132 OH 70 2.115 O 73 1.081 OH 67 2.114 O 82 1.064 OH 60 2.090 O 83 1.089 OH 57 2.147 O 92 1.118 OH 50 2.142 O 93 1.044 OH

28

Magnetic Susceptibility: Magnetic data were collected on ground samples of La-U6, Y-U84, Mn-U70, and Zn-U70 using a Quantum Design Magnetic Property Measurement System (QD-MPMS3). Samples were loaded into VSM Powder Holders, which are near air-tight, in a glovebox and rapidly transferred into the air free chamber of the MPMS, thereby preventing any oxidation of the samples. Zero-field-cooled magnetic susceptibility data were collected from 2 – 300 K under an applied field of 1000 Oe. The raw magnetic moments were corrected for sample shape and radial offset effects.

Figure SI-8A. Magnetic Susceptibility of La-U6

29

Figure SI-8B. Magnetic Susceptibility Y-U84

Figure SI-8C. Magnetic Susceptibility Zn-U70

30

Figure SI-8D. Magnetic Susceptibility of Mn-U70

31

Small Angle X-ray Scattering. SAXS data were collected on an Anton Parr SAXSess instrument utilizing Cu-Ka radiation and line collimation. Data were recorded on an image plate in the range of 0.08-2.5 Å-1. Sample to image plate distance of 26.1 cm. Solutions were measured in 1.5 mm glass capillaries. Tetrahydrofuran/Butylamine (1:3) was used as the background, and scattering was measured for 30 minutes. SAXSQUANT software was used for data collection and processing (normalization, primary beam removal, and background subtraction. The spherical fits of the scattering data were carried out utilizing size distribution and PDDF in the IRENA30 macros within IGOR Pro(9). Simulated scattering curve of the units of the U70 and U84 structure were generated using SolX utilizing structural files (.xyz) containing the selected portion of the structure with no symmetry operations. Simulation of various stacking arrangement and aggregations of the structures were model using Avogrado (10). The U70 solutions were made by dissolving 15 mg of U70-Mn crystals in a solution of 1 mL of 3:1 THF and butylamine. The solutions were then heated at 35 ˚C for 1 h. At which point the solution were filtered using a syringe filter 0.45 µm nylon filter.

Figure SI-9. SAXS data for Mn-U70 (pink) plus core-shell cylindrical fit to data (black line). Parameters for the core-shell fit are summarized in the table and explanation below.

32

Table SI-12. SAXS Parameters1 Core-shell cylinder fitting parameters for Mn-U70 Parameter Value Measured from

crystal structure explanation

cylinder radius 16.2(3) Å 16.0 Å Radius of the U70-ring

cylinder length 103 Å 105 Å length of stack of U70-rings

thickness of cylinder ‘shell’

6.7 Å 7.2 Å Width of U70 ring

Rho of shell 100 (1010 cm-1) N/A X-ray scattering length density of U70 ring

Rho of core 10 (1010 cm-1) N/A X-ray scattering length density of center of U70 ring

Rho of solvent 10 (1010 cm-1) N/A X-ray scattering length density of solvent 1The fit was done in the Irena Macros in IgorPro. All six parameters were refined freely, which compared favorably to the measured distances of a hypothetical stack of eight U70 rings (see figure SI-10 below).

Figure SI-10. Size Distribution analysis of Mn-U70.

33

Infrared Spectroscopy. IR spectra were recorded in attenuated reflectance mode (ATR) using a Thermo Scientific Nicolet iS10 FT-IR spectrometer. The spectra of the following compounds were run. The sulfate peaks were assigned based on Schnaar’s 2012 paper (11), results summarized on Table SI-13. Table SI-13. IR Sulfate Peak Assignments

Crystal Symmetric (A1) (cm-1) Bending (E) (cm-1) Asymmetric (T2) (cm-1) Bending (T2) (cm-1)

(11) 956-1064 407-527 1031-1269 578-669

U(SO4)2 950 580 1127 649

La-U6 1065 510 1065 591

Y-U84 1042 510 1096 591

Mn-U70 1042 537 1075 610

Zn-U70 1043 537 1075 610

Figure-SI-11. IR Spectra

34

Thermogravimetric Analysis: TGA analysis was performed on SDT Q600 TA Instrument in the range of 25˚C-800˚C under argon flow, and at a heating range of 10˚C min-1. TGA analysis was conducted to determine the number of solvent waters. Due to the large void space in each crystal lattice, the samples dehydrate fairly easily and at room temperature, see fig. SI-12. As such we can estimate the number of total waters in the system. By taking the weight difference from the start of the collection to 200 ˚C. Table SI-14 summarizes the results showing partial accounting for the waters. Table SI-14. Calculated Number of Waters by TGA

Total Waters (Calculated) Total Waters (mask + ligands) Crystal

La-U6 30 44.5 Y-U84 248 282.5 Mn-U70 188 407 Zn-U70 129 188

Figure SI-12A. TGA of La-U6

35

Figure SI-12B. TGA of Y-U84

Figure SI-12C. TGA of Zn-U70

100

95

90

85

80

75

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ght P

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nt

600400200

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1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Heat Flow

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)

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95

90

85

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75

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1.5

1.0

0.5

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(mW

)

36

Figure SI-12D. TGA of Mn-U70

100

95

90

85

80

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70

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erce

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600400200

T(C)

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37

References: 1) SAINT Plus Version 8.34a, Bruker Anal. X-rays Syst. Madison, WI2013. 2) G. M. Sheldrick, SADABS, Bruker-Siemens area Detect. Absorpt. other Correct. Version 2008/12008. 3) G. M. Sheldrick, Acta Crystallogr. Sect. A 2015, 71, 3–8. 4) G. M. Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112–122. 5) O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard, H. Puschmann, J. Appl. Crystallogr.2009, 42, 339–341. 6) P. van der Sluis, A. L. Spek, Acta Crystallogr. Sect. A 1990, 46, 194-201 7) L. Glasser. Acta Cryst. B75, 2019, 784-787. 8) L. Glasser. Cryst. Growth Des. 2019, 19, 6, 3397-3401 9) J. Ilavsky and P. R. Jemian, J. Appl. Crystallogr., 2009, 42, 347–353. 10) Avogadro: an open-source molecular builder and visualization tool. Version 1.2.0. http://avogadro.cc/ 11) D. D. Schnaars, R. E. Wilson. Inorg. Chem. 2012, 51, 17, 9481-9490 12) Gagne, O. C. & Hawthorne, F. C. (2015). Acta Cryst. B71, 562-578.

http://avogadro.cc/

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