Acid‐Tolerant Sulfate Tetrahedral Cages from Anion‐Coordination‐Driven Assembly

Zhang, Wenyao; Feng, Yang; Li, Boyang; Yang, Dong; Hou, Le-Kai; Zhao, Wei; Xiao, Yang; Wu, Biao

doi:10.1002/chem.202103671

Cited by 11 publications

(6 citation statements)

References 67 publications

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“…Over the past three years, the nodes of anionocages have been extended from the original (PO 4 3− )-(bisurea) 3 unit to (SO 4 2− )-(bisurea) 3 , 33 (PO 4 3− )-(tisurea) 2 34 and (benzene-1,3,5-tricarboxylate)-(bisurea) 3. 35 In all these cases, two or more urea groups were employed as a dentate of a ligand, while the more readily accessible monourea was never considered as a feasible candidate.…”

Section: Organophosphate Directed Anionocagesmentioning

confidence: 99%

Less is more: from inorganic-phosphate to organophosphate directed anionocages

Sheng,

Yang,

Jia

2023

Mater. Chem. Front.

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Section: Organophosphate Directed Anionocagesmentioning

confidence: 99%

Less is more: from inorganic-phosphate to organophosphate directed anionocages

Sheng,

Yang,

Jia

2023

Mater. Chem. Front.

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Section: Assembly Of Anion Tetrahedral Cagesmentioning

confidence: 99%

“…1,2 Nevertheless, recently, sulfate tetrahedral cages were assembled by using tris-bis(urea) ligands L 11 , L 12 , and L 13 . 29 For L 11 , only a trace of A 4 L 4 species can be detected by mass spectrometry, while the major product is A 3 L 2 (Figure 11b). However, with the larger L 12 and L 13 (Figure 14), the tetrahedron can form in the solid state but exists in solution within a narrow window (depending on the stoichiometric ratio of sulfate to ligand), thus further proving less reliability of sulfate coordination.…”

Section: A 4 L 4 -Type Tetrahedral Cagesmentioning

confidence: 99%

“…The successful assembly of these architectures represents the emergence of “anion-coordination-driven assembly”. In the following 10 years, we have explored this area extensively in guest inclusion, ,− chiral induction, , structural transformation, − photoswitchable conversion, etc. Moreover, the coordination centers have been expanded to sulfate and polycarboxylate anions, which led to much enriched structures and properties.…”

Section: Anion-coordination-driven Assembly (Acda)mentioning

confidence: 99%

“…Nevertheless, recently, sulfate tetrahedral cages were assembled by using tris-bis(urea) ligands L 11 , L 12 , and L 13 . For L 11 , only a trace of A 4 L 4 species can be detected by mass spectrometry, while the major product is A 3 L 2 (Figure b).…”

Section: Assembly Of Anion Tetrahedral Cagesmentioning

confidence: 99%

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Anion-Coordination-Driven Assembly

et al. 2022

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The assembly of discrete architectures has been an important subject in supramolecular chemistry because of their elegant structures and fascinating properties. During the last several decades, supramolecular chemists have developed manifold strategies for hierarchical assembly, which are normally classified by two main types of driving force: covalent and noncovalent interactions. Typical noncovalent interactions include metal coordination, hydrogen bonding, and other weak forces. These approaches have achieved great progress in the construction of various supramolecular structures, such as macrocycles, cages, polyhedra, and interlocked systems. Among these methods, metal-coordination-driven assembly is attractive due to the well-defined coordination properties of metal ions. Indeed, in terms of supramolecular chemistry, the concept of "coordination" has been expanded beyond transition metals. In particular, anion coordination chemistry, which was first proposed by Lehn in 1978 [Acc. Chem. Res. 1978 and then elucidated in detail by Bowman-James two decades later [Acc. Chem. Res. 2005, 38, 671], has grown up to a subfield of supramolecular chemistry. It is noticeable that anions also show "dual valencies" like transition metals, wherein the "primary valence" is the charge balance for anions by countercations while the "secondary valence", i.e., the coordination, refers to hydrogen bonding interactions where the electron flow is from the electron-rich anion (the coordination center) to hydrogen bonding donors (the ligands). Thus, anions also display certain coordination numbers and specific coordination geometries. Although such features are far less regular than those of transition metals, they are sufficient to allow anion coordination to serve as the driving force for assembling discrete supramolecular architectures. In this Account, the anion-coordination-driven assembly (ACDA), a new assembling strategy established by us during the past decade, will be presented. We summarize our work in the construction of a series of "aniono" supramolecular structures, especially triple helicates and tetrahedral cages, based on the coordination between oligourea ligands and anions (mostly phosphate). In particular, we will detail the considerations in the design of ligands, the assembling process including structural transformation, and functionalization of the systems toward guest inclusion, supramolecular catalysis, photoswitches, and molecular devices. These results demonstrate the great potential of ACDA in fabricating novel anion-based systems. Although the design concept was originally loaned from traditional coordination chemistry of transition metals, and structures of anion complexes bear some resemblance to metal complexes, there are significant differences of the aniono supramolecular assemblies from the metallo analogues. For example, these metal-free systems are held together by multiple hydrogen bonds (dozens to nearly 100), thus facilitating assembly/disassembly under mild conditions and relatively flexible s...

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A Hydrogen‐Bonded Ravel Assembled by Anion Coordination

Zhao

Wang

et al. 2021

Angewandte Chemie

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Anion‐coordination‐driven assembly (ACDA) is showing increasing power in the construction of anionic supramolecular architectures. Herein, by expanding the anion centers from oxoanion (phosphate or sulfate) to organic tris‐carboxylates, an Archimedean solid (truncated tetrahedron) and a highly entangled, double‐walled tetrahedron featuring a ravel topology have been assembled with tris‐bis(urea) ligands. The results demonstrate the promising ability of tris‐carboxylates as new anion coordination centers in constructing novel topologies with increasing complexity and diversity compared to phosphate or sulfate ions on account of the modifiable size and easy functionalization character of these organic anions.

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Acid‐Tolerant Sulfate Tetrahedral Cages from Anion‐Coordination‐Driven Assembly

Cited by 11 publications

References 67 publications

Less is more: from inorganic-phosphate to organophosphate directed anionocages

Less is more: from inorganic-phosphate to organophosphate directed anionocages

Anion-Coordination-Driven Assembly

A Hydrogen‐Bonded Ravel Assembled by Anion Coordination

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