The Construction of High‐Nuclearity Isopolyoxoniobates with Pentagonal Building Blocks: [HNb27O76]16− and [H10Nb31O93(CO3)]23−

Tsunashima, Ryo; Long, De‐Liang; Miras, Haralampos N.; Gabb, David; Pradeep, Chullikkattil P.; Cronin, Leroy

doi:10.1002/ange.200903970

Cited by 45 publications

(43 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Die neuen Strukturen und Syntheseansätze auf diesem Gebiet könnten den üblicherweise inerten Nb-Zentren neue physikalische Eigenschaften verleihen, insbesondere in den von uns entdeckten Strukturen mit fünfeckigen Einheiten. [32] Während die Klassifizierung von POM-Clustern sehr nützlich sein kann (Abbildung 2), werden die Richtlinien ständig durch neue Synthesen und Strukturen infrage gestellt. So sind die Peroxo-Uran-Verbindungen zwar nicht-klassische POM-Cluster, sie zeigen aber einige wichtige Analogien, insbesondere mit größeren Strukturen.…”

Section: Synthesestrategienunclassified

Polyoxometallate als Bausteine für funktionelle Nanosysteme

2010

Self Cite

View full text Add to dashboard Cite

Die Polyoxometallate (POM), eine Untergruppe der Metalloxide, bilden vielfältige Molekülcluster, die nicht nur außerordentlich vielfältige physikalische Eigenschaften zeigen, sondern auch dynamische Strukturen mit Abmessungen vom Nanometer‐ bis zum Mikrometermaßstab bilden können. Hier beschreiben wir die neuesten Entwicklungen von der Synthese bis zur Struktur und Funktion von Polyoxometallaten. Wir diskutieren Wege zur Herstellung höchst differenzierter hierarchischer Systeme mit mehreren voneinander unabhängigen Funktionalitäten und geben eine kritische Analyse, aus der auch nichtspezialisierte Leser die wichtigsten Eigenschaften ersehen können. In diesem Zusammenhang schlagen wir auch ein “Periodensystem der Polyoxometallat‐Baueinheiten” vor. Schließlich beleuchten wir einige aktuelle Herausforderungen beim Design funktioneller Systeme auf der Basis von POM‐Baueinheiten und geben einen Ausblick auf mögliche Anwendungen.

show abstract

Section: Synthesestrategienunclassified

Polyoxometallate als Bausteine für funktionelle Nanosysteme

2010

Self Cite

View full text Add to dashboard Cite

show abstract

“…[5] However, great progress has been made in polyoxoniobate chemistry in recent years owing to the discovery and development of heteropolyniobates by Nyman and co-workers, [6] the research presented by Casey and co-workers, [7] and the recent reports on [Nb 20 O 54 ] 8À , [8] [H 9 Nb 24 O 72 ] 15À , [9] [Nb 7 O 22 ] 9À , [10a] [{Cu-A C H T U N G T R E N N U N G (H 2 O)L} 2 (CuNb 11 O 35 H 4 )] 5À (L = 1,10-phenanthroline, 2,2'-bipyridine), [10b] [HNb 27 O 76 ] 16À and [H 10 Nb 31 O 92 A C H T U N G T R E N N U N G (CO 3 )] 23À . [11] However, the development of polyoxoniobate chemistry is still at an early stage and is dominated by reactions performed under alkaline and mainly hydrothermal conditions. The potential of polyoxoniobates is expected to be explored in acidic solution in which other POMs and transition-metal and lanthanide ions widely exist.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Polyoxoniobates in Acidic Solution: Controllable Assembly and Disassembly Based on Niobium‐Substituted Germanotungstates

Liu

et al. 2010

Chemistry A European J

View full text Add to dashboard Cite

The reactivity of polyoxoniobates has been studied in acidic solution by grafting niobium onto trivacant Keggin-type germanotungstates. Four niobium-containing compounds were obtained in the course of this study. Cs(6.5)K(0.5)[GeW(9)(NbO(2))(3)O(37)]·6H(2)O (Cs(6.5)K(0.5)-1) synthesized by the reaction of K(7)H[Nb(6)O(19)] and A-α-Na(10)[GeW(9)0(34)] in H(2)O(2) solution is a tris(peroxoniobium)-substituted A-α-GeW(9) derivative. Cs(6.5)K(0.5)[GeW(9)Nb(3)O(40)]·10H(2)O (Cs(6.5)K(0.5)-2) is a peroxo-free compound obtained by eliminating the peroxo groups in 1. Monomers 1 and 2 as precursors can each afford two nanoscale POMs, dimer Cs(5)[H(15)Ge(2)W(18)Nb(8)O(88)]·18H(2)O (Cs(5)-3) and tetramer Cs(8)K(3)H(9)[Ge(4)W(36)Nb(16)O(166)]·27H(2)O (Cs(8)K(3)H(9)-4), through the formation of Nb-O-Nb bridges. Disassembly through the cleavage of Nb-O-Nb bonds from 4 to 2 and 1 was achieved by controlling the pH and by adding H(2)O(2), respectively. The transition from 1 to 2 can be achieved by simply adding H(2)O(2) to a solution of 1. All four compounds were characterized in the solid state by elemental analysis, infrared spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. (183)W NMR analysis proved that the solid-state structures of polyanions 1-4 were retained after dissolution. Disassembly from 4 to 1 and 2 in solution was observed by (183)W NMR spectroscopy. The UV/Vis spectra of 1 at different pH confirmed that it is stable in the pH range of 0.1-14.0 at room temperature.

show abstract

“…6). 30a Further, we attempted to 10 introduce the vanadium clusters into the HPON (Fig. 7), and Na{Cu (en) cluster-substituted HPONs.…”

Section: Heteropolyniobates Decorated By Tm Cationsmentioning

confidence: 99%

“…5 For a long time, only the 45 Lindquist-type PON [Nb 6 O 19 ] 8was studied, and it has been isolated as the Cs, K, Na, Li and their mixed salts. 6 Twenty-four years later, the synthesis and structural characterization of a decaniobate anion [Nb 10 O 28 ] 6was reported in the literature. 7a Subsequently, a colorless crystalline icosaniobate [Nb 20 O 54 ] 8- 50 was isolated as the tetra-n-butylammonium salt.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Recent progress in polyoxoniobates decorated and stabilized via transition metal cations or clusters

Wang

Zhang

et al. 2015

CrystEngComm

View full text Add to dashboard Cite

5Transition-metal (TM) cations and clusters have been widely used to functionalize polyoxometalates (POMs) of the tungsten, molybdenum and vanadium, as their acidic nature, which made them compatible with addendum TM cations. Together with the well understanding of their solution behavior, a great achievement of TM-based POMs has been made, which exhibited potential applications in many fields. Comparably, fewer polyoxoniobates (PONs) were obtained as the poor understanding of their solution 10 behavior, and they could only exist in the strong alkaline aqueous solution, where most of the TM cations precipitated as the formation of hydroxide or oxide. Recently, the TM cations were introduced into the PONs by protection of the chelate organic ligands or via selection of the alkaline-soluble TM cations. Further, lacunary POMs, composed of early TM cations, were used as the polydentate ligands to isolate the PONs, and they make the PON clusters stably exist in the acidic solution. The acidic nature of the 15 tungstoniobate (W-Nb) clusters allowed acid-soluble TM cations to directly functionalize the Nb-W clusters. This highlight focuses on discussing the roles of the TM centers in constructing the PON-based materials, including the TM-cluster-containing PONs, TM-organic group-decorating PONs and the niobate clusters isolated by lacunary POMs. The systemically compilation of TM-PON work will reveal a promising direction for further functionalization of the PONs, and it will be more rich and diverse of the 20 PON chemistry.

show abstract

The Construction of High‐Nuclearity Isopolyoxoniobates with Pentagonal Building Blocks: [HNb₂₇O₇₆]¹⁶⁻ and [H₁₀Nb₃₁O₉₃(CO₃)]²³⁻

Cited by 45 publications

References 35 publications

Polyoxometallate als Bausteine für funktionelle Nanosysteme

Polyoxometallate als Bausteine für funktionelle Nanosysteme

Reactivity of Polyoxoniobates in Acidic Solution: Controllable Assembly and Disassembly Based on Niobium‐Substituted Germanotungstates

Recent progress in polyoxoniobates decorated and stabilized via transition metal cations or clusters

Contact Info

Product

Resources

About