Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

Chen, Linfeng; Turo, Michael J.; Gembický, Milan; Reinicke, Ruth A.; Schimpf, Alina M.

doi:10.1002/ange.202005627

“…[19][20] Building-block synthetic approaches have been hypothesized in metal-oxo systems including; 1) assembly of Pd84 and Pd72 Pd-oxo toroids from a Pd6 fragment; [21][22][23] 2) Mn84 and Mn70 built from a Mn12 oxo-acetate; [24][25] 3) growth of giant molybdate POMs from smaller clusters; 26-27 4) assembly of successively larger Lnx species (x = 12-140) from a Ln4 oxocluster building unit; 18,[28][29][30][31] , 5) isolation of various sized LnxNiyoxoclusters (up to 164 metal polyhedra) from smaller oxocluster building blocks, 15,[32][33] and 6) capping and linking of POMs into rigid chains and frameworks, and flexible polymers. [34][35][36] The d-block and f-block tetravalent metal cations (M IV =Zr/Hf/Ce/U/Np/Pu IV ) are amongst the most studied metal-oxo cluster families. Of special note, Zr/Hf MOFs are built of the M6(OH,O)8 hexamer (M6), and these MOFs are widely exploited for virtually every application that has been developed to date including catalysis and separations.…”

Section: Introductionmentioning

confidence: 99%

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Colliard

¹

,

Brown

²

,

Fast

³

et al. 2021

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Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [Ce IV 70(OH)36(O)64(SO4)60(H2O)10] 4-, part of a larger emerging family of M IV 70materials (M=Zr, U, Ce), presents such an opportunity. We have elucidated assembly mechanisms by X-ray scattering (small-angle scattering and total scattering) of solutions and solids, as well as crystallizing and identifying fragments of Ce70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce5, [Ce5(O)3(SO4)12] 10-) and modular assembly from hexamer (Ce6) building units (Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6and Ce62, [Ce62(OH)30(O)58(SO4)58] 14-). Ce62, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH4 + , which can also be replaced by other cations, demonstrated with Ce III . Room temperature rapid assembly of both Ce70 and Ce62, respectively, by addition of Li + and NH4 + , along with ionexchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications. Ce70, [Ce IV 70(OH)36(O)64(SO4)60] 4-, was described prior, and is also isostructural with Zr70 and U70. [49][50][51][52] Briefly, the Ce70 cluster can be viewed as ten Ce6-hexamers that alternate with ten Ce1-monomers. Four sulfates bridge each Ce6 and Ce1 along the outer rim, and four additional sulfates bridge only Ce6 units along the inner rim. Each fragment discussed later can be viewed in the same context. The Ce62, [Ce62(OH)30(O)58(SO4)58] 14-, consisting of ~90% of the ring, contains nine Ce6 and eight Ce1. Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6-, consists of two Ce6 and Ce1, and is approximately 20% of the ring. Ce5 [Ce5(O)3(SO4)12] 10-, resembles half of the Ce6 plus two flanking monomers. These clusters and their intrinsic relation to the Ce70, summarized in figure 1, serve as crystallographic snapshots of mechanistic pathways for ring formation.

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“…[19][20] Building-block synthetic approaches have been hypothesized in metal-oxo systems including; 1) assembly of Pd84 and Pd72 Pd-oxo toroids from a Pd6 fragment; [21][22][23] 2) Mn84 and Mn70 built from a Mn12 oxo-acetate; [24][25] 3) growth of giant molybdate POMs from smaller clusters; 26-27 4) assembly of successively larger Lnx species (x = 12-140) from a Ln4 oxocluster building unit; 18,[28][29][30][31] , 5) isolation of various sized LnxNiyoxoclusters (up to 164 metal polyhedra) from smaller oxocluster building blocks, 15,[32][33] and 6) capping and linking of POMs into rigid chains and frameworks, and flexible polymers. [34][35][36] The d-block and f-block tetravalent metal cations (M IV =Zr/Hf/Ce/U/Np/Pu IV ) are amongst the most studied metal-oxo cluster families. Of special note, Zr/Hf MOFs are built of the M6(OH,O)8 hexamer (M6), and these MOFs are widely exploited for virtually every application that has been developed to date including catalysis and separations.…”

Section: Introductionmentioning

confidence: 99%

Snapshots of Ce70 Toroid Assembly from Solids and Solution

Colliard¹,

Brown²,

Fast³

et al. 2021

Preprint

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Crystallization at the solid-liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [CeIV70(OH)36(O)64(SO4)60(H2O)10] 4- , part of a larger emerging family of MIV70- materials (M=Zr, U, Ce), presents such an opportunity. We have elucidated assembly mechanisms by X-ray scattering (small-angle scattering and total scattering) of solutions and solids, as well as crystallizing and identifying fragments of Ce70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce5, [Ce5(O)3(SO4)12] 10- ) and modular assembly from hexamer (Ce6) building units (Ce13, [Ce13(OH)6(O)12(SO4)14(Η2Ο)14] 6- and Ce62, [Ce62(OH)30(O)58(SO4)58] 14- ). Ce62, an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH4 +, which can also be replaced by other cations, demonstrated with CeIII. Room temperature rapid assembly of both Ce70 and Ce62, respectively, by addition of Li+ and NH4 +, along with ion?exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.

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“…Moreover, counter-cations play primary roles in the assembly of any oligomeric species in the crystallization process. [61][62][63][64] Combining first-row transition metals with Ce IV (SO4)2 and heating at 75 °C (see SI for details) promotes assembly of the Ce70 torus cluster; fully formulated [Ce IV (OH)36(O)64(SO4)60(H2O)10] 4-, isostructural with prior reported U70 (Figure 1a). 26,59 Analogous to U70, the Ce70 cluster can be viewed as alternating Ce6 and Ce1; four sulfates bridge a Ce6 and a Ce1 along the outer rim, and four additional sulfate line the inner rim bridging only between Ce6, see Figure 1b.…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

Colliard¹,

Nyman²

2020

Preprint

0

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MIV molecular oxo-clusters of the f- and d-block (M=Zr, Hf, Ce, Th, U, Np, Pu) have been prolific in bottoms-up material design, catalysis, as well as understanding metal oxide assembly, dissolution and surface reactivity in nature and in synthesis. Here we introduce Ce70, a new CeIV wheel-shaped oxo-cluster, [CeIV(OH)36(O)64(SO4)60(H2O)10]4-, isostructural with prior-reported U70. Like U70, Ce70 crystallizes into intricate frameworks with divalent transition metal counter-cations (TMII), and also CeIV-monomer and sulfate addenda ions.

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Cation‐Controlled Assembly of Polyoxotungstate‐Based Coordination Networks

Cited by 28 publications

References 64 publications

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Snapshots of Ce₇₀ Toroid Assembly from Solids and Solution

Snapshots of Ce70 Toroid Assembly from Solids and Solution

Supramolecular Assembly of CeIV-Oxo Sulfate Torus with Transition Metal Countercations

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