High‐dimensional Polyoxoniobates Constructed from Lanthanide‐incorporated High‐nuclear {[Ln(H2O)4]3[Nb24O69(H2O)3]2} Secondary Building Units

Zhang, Jing; Lai, Rong-Da; Wu, Yan‐Lan; Zhu, Zeng‐Kui; Sun, Yan‐Qiong; Zeng, Qingxin; Li, Xin‐Xiong; Zheng, Shou‐Tian

doi:10.1002/asia.202000294

“…Frameworks of mixed Nb/W‐ POMs decorated with La 3+ have been isolated, enabled by the higher acidity of mixed Nb/W‐POMs [21] . Most recently Zheng reported a cluster assembly featuring Nb 24 ‐dimers linked by rare‐earth cations (Dy and Eu), [22] and also Cu‐en complexes. These structures are similar to Cs‐Nb 24 reported here, with the Ln 3+ acting as a countercation, replacing the Cs + .…”

Section: Resultsmentioning

confidence: 99%

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Amiri

¹

,

Martin

²

,

Feng

³

et al. 2021

Angewandte Chemie

8

0

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Polyoxometalates (POMs, metals=VV, NbV, TaV, MoVI, WVI) are molecular metal oxides that can be isolated without capping ligands. The high negative charge of polyoxoniobates (PONb) provides strong interactions with heterocations, advantageous for electrostatic assembly of modular materials. In four single‐crystal X‐ray structures, we demonstrate that carbonate combined with the very reactive decaniobate [Nb10O28]6− reassembles into a new decaniobate, [Nb10O25(CO3)6]12−, featuring three carbonate‐ligated Nb‐polyhedra. These Nb‐sites can be replaced by heterometals (lanthanides), and the tridentate carbonate can serve as an anchor point to build niobate‐frameworks. Small‐angle X‐ray scattering and two additional X‐ray structures reveal that the reaction pathway proceeds through a Nb24‐PONb intermediate, and the obtained PONb (with or without carbonate) is counterion, temperature, and solvent‐dependent (water or mixed water‐methanol). This provides an uncommon level of control for PONb chemistry.

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“…[17][18][19] Va nadium-substituted PONbs linked by transition metal coordination complexes form 3D hybrid organic-inorganic frameworks. [20][21][22] More recently,t here has been considerable interest in the [Nb 24 ] PONb,a nd it has been linked into 1D chains with lanthanides, [23,24] and 3D networks with Cu complexes. [25][26][27][28] Decaniobate ([Nb 10 O 26 ] 6À [Nb 10 ]; Figure 1) is an unusual PONb,s table at neutral pH.…”

Section: Introductionmentioning

confidence: 99%

Directional Bonding in Decaniobate Inorganic Frameworks

Nyman

¹

,

Martin

²

2020

Angewandte Chemie

6

0

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Metal–oxo clusters offer an opportunity to assemble inorganic and metal–organic frameworks (MOFs) by a controlled building‐block approach, which led to the revolutionary discoveries of zeolites and MOFs. Polyoxometalate clusters are soluble in water, but more challenging to link into frameworks; the inert oxo‐caps that provide solubility are resistant to replacement or further connectivity. We demonstrate how the unique directional bonding and varying basicity of the decaniobate ([Nb10]) oxo‐caps can be exploited to build 1D, 2D, and 3D inorganic frameworks. In nine structures, A+ (A=Li, Na, K, Rb and Cs), AE2+ (AE=Ca, Sr, Ba) and Mn2+ demonstrate that the dimensionality of the obtained material is controlled by cation charge and size. Increased cation charge decreases selectivity for oxo‐site bonding, leading to higher dimensional linking. Larger cation radii also decreases bonding selectivity, yielding higher dimensional materials. Ion‐exchange studies of the A+‐Nb10 family shows exclusive selectivity for Cs+ over other alkalis, which is important for radioactive Cs removal and sequestration.

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Directional Bonding in Decaniobate Inorganic Frameworks

Martin

¹

,

Nyman

²

2020

View full text Add to dashboard Cite

Metal–oxo clusters offer an opportunity to assemble inorganic and metal–organic frameworks (MOFs) by a controlled building‐block approach, which led to the revolutionary discoveries of zeolites and MOFs. Polyoxometalate clusters are soluble in water, but more challenging to link into frameworks; the inert oxo‐caps that provide solubility are resistant to replacement or further connectivity. We demonstrate how the unique directional bonding and varying basicity of the decaniobate ([Nb10]) oxo‐caps can be exploited to build 1D, 2D, and 3D inorganic frameworks. In nine structures, A+ (A=Li, Na, K, Rb and Cs), AE2+ (AE=Ca, Sr, Ba) and Mn2+ demonstrate that the dimensionality of the obtained material is controlled by cation charge and size. Increased cation charge decreases selectivity for oxo‐site bonding, leading to higher dimensional linking. Larger cation radii also decreases bonding selectivity, yielding higher dimensional materials. Ion‐exchange studies of the A+‐Nb10 family shows exclusive selectivity for Cs+ over other alkalis, which is important for radioactive Cs removal and sequestration.

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High‐dimensional Polyoxoniobates Constructed from Lanthanide‐incorporated High‐nuclear {[Ln(H₂O)₄]₃[Nb₂₄O₆₉(H₂O)₃]₂} Secondary Building Units

Abstract: In this work, two rare high-dimensional polyoxoniobates with formulas of H 9 [Cu(en)

Cited by 17 publications

References 50 publications

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Deliberate Construction of Polyoxoniobates Exploiting the Carbonate Ligand

Directional Bonding in Decaniobate Inorganic Frameworks

Directional Bonding in Decaniobate Inorganic Frameworks

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