Benzene Triimides: Facile Synthesis and Self‐Assembly Study

Tuo, De‐Hui; He, Qing; Wang, Qi‐Qiang; Ao, Yu‐Fei; Wang, De‐Xian

doi:10.1002/cjoc.201900146

Cited by 8 publications

(14 citation statements)

References 38 publications

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“…Apart from triazine and tetrazine, benzene triimide (BTI) also appears to be an ideal π receptor for anion recognition due to its electron-deficient π system ( Q zz = 14.5 B) . We have recently synthesized a triangular prism cage 33 containing two face-to-face BTIs pillared by meta -xylylene units (Scheme ).…”

Section: Anion–π Interactions In Selective Recognition Of Anionsmentioning

confidence: 99%

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Wang

2020

Acc. Chem. Res.

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 Selective Recognition Of Anionsmentioning

confidence: 99%

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Wang

2020

Acc. Chem. Res.

140

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“…Structural Study of the Obtained CT Complexes BTI-Me was synthesized through the reported procedure described. [6] The cyclic voltammograms of BTI-Me in DMSO were previously reported with three reversible redox waves corresponding to their reduction. [6] The first reduction potential was À 1.04 V vs. Fc/Fc + , which indicates that BTI-Me can be reduced by CoCp 2 [14] and electrochemical crystallization methods are also accessible.…”

Section: Resultsmentioning

confidence: 98%

Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array

et al. 2022

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Benzenetriimide (BTI) is a promising building block for materials chemistry due to its characteristic 3-fold symmetry and redox properties, whereas little is known about its conductive and magnetic properties. In this study, we synthesized three chargetransfer complexes based on N,N',N''-trimethylbenzenetriimide (BTI-Me). One of the complexes contains isolated dimers of BTI-Me radical anion (BTI-Me *À ), while the other two have the infinite π-stacked array of BTI-Me with the formal charge of À 0.5. The latter two complexes did not show metallic behavior but showed semiconducting behavior probably due to the characteristic insulation in one-dimensional electron system, socalled charge ordering and dimer-Mott insulation. The magnetic susceptibility of the complex in dimer-Mott state exhibits an unusual transition from antiferromagnetic to ferromagnetic spin states with the hysteresis loop of 15 K derived from the structural phase transition around 130 K. These properties were also supported by DFT calculations.

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“…This limited attention could be due to difficulties in the synthesis of BTI‐related compounds. Recently, we developed a facile synthetic protocol to access a variety of BTI derivatives and explored their electrochemical properties . We envisioned that the intriguing C 3 symmetry and high π acidity of BTI would make it a promising basic unit for magnetic materials.…”

Section: Methodsmentioning

confidence: 99%

Magnetic Multistability in an Anion‐Radical Pimer

et al. 2020

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Radical pimers are the simplest and most important models for studying charge-transfer processes and provide deep insight into p-stacked organic materials. Notably, radical pimer systems with magnetic bi-or multistability may have important applications in switchable materials, thermal sensors, and information-storage media. However, no such systems have been reported. Herein, we describe a new pimer consisting of neutral N-(n-propyl) benzene triimide ([BTI-3C]) and its anionic radical ([BTI-3C] À C) that exhibits rare magnetic multistability. The crystalline pimer was readily synthesized by reduction of BTI-3C with cobaltocene (CoCp 2). The transition occurred with a thermal hysteresis loop that was 27 K wide in the range of 170-220 K, accompanied by a smaller loop with a width of 25 K at 220-242 K. The magnetic multistability was attributed to slippage of the p-stacked BTI structures and entropy-driven conformational isomerization of the side propyl chains in the crystalline state during temperature variation. Cation and anion radicals (M +

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Benzene Triimides: Facile Synthesis and Self‐Assembly Study

Cited by 8 publications

References 38 publications

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Exploring Anion−π Interactions and Their Applications in Supramolecular Chemistry

Benzenetriimide‐Based Molecular Conductor with Antiferro‐ to Ferromagnetic Switching Induced by Structural Change of π‐stacked Array

Magnetic Multistability in an Anion‐Radical Pimer

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