Macrocycle‐Directed Construction of Tetrahedral Anion–π Receptors for Nesting Anions with Complementary Geometry

Luo, Jian; Zhu, Jun; Tuo, De‐Hui; Yuan, Qinqin; Wang, Lei; Wang, Xuebin; Ao, Yu‐Fei; Wang, Qi‐Qiang; Wang, De‐Xian

doi:10.1002/chem.201903272

Cited by 16 publications

(8 citation statements)

References 80 publications

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“…To obtain binding selectivity for tetrahedral and octahedral anions, cage 8 embedding four tetrahedrally disposed triazine rings was synthesized (Scheme 3). 24 As shown by SCXRD, four triazine rings in 8 indeed form an electrondeficient tetrahedral cavity. Gratifyingly, it complexes preferentially with tetrahedral and octahedral anions.…”

Section: Anion−π Interactions In Selectivementioning

confidence: 99%

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Wang

2020

Acc. Chem. Res.

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140

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Metrics & MoreArticle Recommendations CONSPECTUS: Noncovalent bond interactions provide primary driving forces for supramolecular processes ranging from molecular recognition to self-assembly of sophisticated abiotic and biological machineries. While hydrogen bonding and π−π interactions are arguably textbook concepts playing indispensable parts in various scientific disciplines, noncovalent anion−π interactions have been emerging as attractive forces between π systems and negatively charged species for just about two decades. At the beginning of this century, three research groups reported independently their computational studies on the interactions between anions and aromatic compounds, proposing attractive anion−π interactions. Since π systems such as aromatic rings are traditionally noted as electron rich entities, anions and π systems would be repulsive to each other if there are any interactions. In stark contrast to the acknowledged cation−π interactions, the seemingly counterintuitive noncovalent anion−π bindings invoked great interest in the following years. Although a plethora of calculations had been published, the lack of experimental evidence cast doubt on the existence of anion−π interactions between anions and charge-neutral aromatic systems.During the same time when anion−π interactions were coined, we were studying the chemistry of novel macrocyclic compounds, namely, heteracalixaromatics, and their applications in supramolecular chemistry. It has been shown that heteracalixaromatics are powerful and versatile macrocyclic hosts to bind various guest species forming interesting assembled structures and organometallic complexes. Being a member of heteracalixaromatics, tetraoxacalix[2]arene[2]triaizne adopts a 1,3-alternate conformational structure yielding a V-shaped cavity or cleft formed by two electron-deficient triazine rings. Advantageously, the macrocycle is able to self-tune the cavity sizes by altering the degrees of conjugation between the bridging oxygen atoms with their bonded aromatic rings in response to the guest species in present, rendering it an ideal tool to explore anion−π interactions. We initiated our study on anion−π interactions using tetraoxacalix[2]arene[2]triazine as a molecular tool with the primary aim to clarify experimentally the uncertainty of whether exclusive anion−π interactions exist between anions and charge-neutral aromatic rings. We provided for the first time concrete evidence substantiating the formation of typical anion−π interaction between the anions and 1,3,5-triazine ring and demonstrated subsequently the generality and binding motifs of anion−π interactions. We have then extended our study to anion−π interaction-directed or -driven anion recognition and selective sensing, transmembrane anion transport, molecular selfassembly, and stimuli-responsive aggregation systems. A number of new generation macrocycles and cages constructed from electron-deficient tetrazine and benzenetriimide segments have also been developed in the meantime, advancing the study ...

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Section: Anion−π Interactions In Selectivementioning

confidence: 99%

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Wang

2020

Acc. Chem. Res.

Self Cite

140

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“…[29][30][31] Among them, the motif c is suggested to be most energetically favorable. However, while the less stable motifs a and b have been frequently observed in crystal structures of complexes [26][27][28][32][33][34][35][36] and in biological anion- pairs, 21 the most stable motif c has barely been found. In the meantime, the subtle difference in the binding motifs could cause a large influence on relevant functions, e.g., catalysis 37,38 or macromolecular structuring.…”

Section: Introductionmentioning

confidence: 97%

“…However, the strength of anion- interactions involving polyhedral, e.g., tetrahedral or octahedral anions is generally weak owing to the large size and low electron density of these anions. [26][27][28] On the other hand, the polyhedral shape of anions would in principle lead to diverse binding motifs when the anion approaches above an aromatic  surface. Indeed, theoretical calculation suggested different binding motifs (motifs a, b, c in Figure 1) exist, with different binding energy, binding geometry and anion- interacting distance.…”

Section: Introductionmentioning

confidence: 99%

Naphthalene-Pillared Benzene Triimide Cage: An Efficient Receptor for Polyhedral Anions and a General Tool for Probing Theoretically-Existing Anion-π Binding Motifs

Tuo¹,

Ao²,

Wang³

et al. 2022

CCS Chem

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A triangular prism cage 2 with benzene triimide (BTI) as the bases, 2,7-naphthalene dimethyl as the supporting pillars was designed and synthesized efficiently. The two parallel BTI planes constitute a cavity of 7.58 Å which allows inclusion of anions of various sizes. Cage 2 showed so far the strongest binding affinity to a series of polyhedral (tetrahedral and octahedral) anions including PF 6 -(24651 M -1 ), ClO 4 -(28234 M -1 ), CH 3 SO 3 -(30571 M -1 ), BF 4 -(31613 M -1 ) and HSO 4 -(84623 M -1 ). The obtained eleven crystal structures of 2⸧Xcomplexes with different anions demonstrated that multiple and cooperative anion- interactions contribute synergistically to the strong complexation. The series of complex structures systematically suggested that cage 2 is a good, general tool for probing anion- binding motifs that have only been predicted in theoretical calculations. For anions of triangular (NO 3 -) and polyhedral (BF 4 -, ClO 4 -, PF 6 -) shapes, the as-predicted most stable anion- binding motifs with charge-neutral  systems were experimentally observed for the first time.

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“…One possible approach to achieve greater selectivity and affinity is to design receptors that can coordinate all four oxygen atoms of the tetrahedral anion. Such an approach haas been already implemented for recognition of sulfate and phosphate anions resulting in a highly selective binding [35][36][37][38][39][40][41][42].…”

Section: Introductionmentioning

confidence: 99%

Helix-Like Receptors for Perrhenate Recognition Forming Hydrogen Bonds with All Four Oxygen Atoms

et al. 2021

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Supramolecular recognition of perrhenate is a challenging task due to therelatively large size and low charge density of this anion. In this work, we design and synthesize a family of helix-like synthetic receptors that can bind perrhenate by forming hydrogen bonds with all four oxygen atoms of the anion. Among the investigated rigid helix-forming subunit derived from 1,1′-ferrocenedicarboxylic acid, 1,3-phenylenediacetic acid and 2,2′-(ethyne-1,2-diyl)dibenzoic acid, the latter one shows the best selectivity for perrhenate recognition. However, the receptor based on 1,1′-ferrocenedicarboxylic acid demonstrates selectivity to bind chloride in a 1:2 fashion. The properties of the receptors are investigated in the acetonitrile solution by using NMR, UV–Vis, and in the solid state by single crystal X-ray analysis.

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Macrocycle‐Directed Construction of Tetrahedral Anion–π Receptors for Nesting Anions with Complementary Geometry

Cited by 16 publications

References 80 publications

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Naphthalene-Pillared Benzene Triimide Cage: An Efficient Receptor for Polyhedral Anions and a General Tool for Probing Theoretically-Existing Anion-π Binding Motifs

Helix-Like Receptors for Perrhenate Recognition Forming Hydrogen Bonds with All Four Oxygen Atoms

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