Complexation Between (<i>O</i>‐Methyl)<sub>6</sub>‐2,6‐Helic[6]arene and Tertiary Ammonium Salts: Acid/Base‐ or Chloride‐Ion‐Responsive Host–Guest Systems and Synthesis of [2]Rotaxane

Shi, Qiang; Han, Ying; Chen, Chuan‐Feng

doi:10.1002/asia.201700857

Cited by 16 publications

(8 citation statements)

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“…We proved (±)- 55 could encapsulate protonated tertiary ammonium guests 68a – h to form 1:1 complexes and also found that small substituent groups on the N atoms or an electron-withdrawing group on the aromatic ring of the guests could be beneficial for the host–guest complexation. Especially, the switchable complexation between the macrocycle and the ammonium guests could be efficiently controlled by acid/base stimuli (Figure a) and also by the addition and removal of chloride ion (Figure b).…”

Section: Helicarenes: New Chiral Macrocyclic Arenesmentioning

confidence: 99%

Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes

2018

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The development of new types of synthetic macrocyclic hosts is always one of the most important and attractive topics in macrocyclic and supramolecular chemistry. Calixarenes, resorcinarenes, cyclotriveratrylenes, pillararenes, and their analogues are all composed of hydroxy-substituted aromatic rings bridged by methylene or methenyl groups and thus can be considered a type of macrocyclic arenes. Because of their unique structural features, easy functionalization, and wide applications in many research areas, such macrocyclic arenes have become some of the most important and studied synthetic macrocyclic hosts during the last decades. Triptycene and its derivatives are a class of organic molecules having unique three-dimensional rigid structures, and they have proved to be useful building blocks for constructing new synthetic macrocyclic hosts with specific structures and properties. Dihydroxy-substituted triptycene derivatives are readily available compounds, which encouraged us to conduct studies of triptycene-derived macrocyclic arenes about 10 years ago. Consequently, a series of triptycene-derived calixarenes and analogues containing 1,8-dihydroxy-substituted triptycene subunits were conveniently synthesized. With 2,7-dihydroxy-substituted triptycene as a precursor, new types of calixarene, oxacalixarene, and homooxacalixarene analogues were also obtained. These triptycene-derived macrocyclic hosts all showed fixed conformations in solution and exhibited expanded cavities compared with the corresponding typical calixarenes and analogues. The special structural features also make these triptycene-derived macrocycles show wide potential applications in molecular recognition and self-assembly. In particular, it was found that the threading direction and the orientation based on macrocycles with nonsymmetric structures could be finely controlled by adjusting the electrostatic and steric effects of the guests, which could form the oriented [2]rotaxane by unidirectional threading. We recently developed a new kind of chiral macrocyclic arenes named helicarenes that are composed of chiral 2,6-dihydroxy-substituted triptycene subunits bridged by methylene groups. It was found that the helicarenes not only exhibited convenient synthesis, high stability, good solubility, fixed conformations, and easy functionalization but also showed complexation abilities with various chiral and achiral organic guests. In particular, the switchable complexation based on these macrocycles could be efficiently controlled by multiple stimuli, including acid/base, redox, anion, or light stimuli under a photoacid. Moreover, the helicarenes have also found applications in the construction of interlocked molecules and molecular machines. This Account summarizes our recent research results on the synthesis and structures of the triptycene-derived macrocyclic arenes and analogues and their applications in host-guest chemistry and molecular assembly. We believe that these macrocyclic arenes, especially helicarenes, could be utilized as new synt...

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Section: Helicarenes: New Chiral Macrocyclic Arenesmentioning

confidence: 99%

Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes

2018

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“…General Information: ( O ‐Methyl) 6 ‐2,6‐helic[6]arene ( HA ), Compound 1 and 5 were prepared according to literature procedure. [12a], , Other reagents were commercially available and used without further purification. Flash column chromatography was performed on 200– 300 mesh silica gel.…”

Section: Methodsmentioning

confidence: 99%

“…It was found that helicarenes exhibited extensive recognition towards different kind of ammonium salts, N‐heterocyclic salts, the tropylium cation and neutral electron‐deficient molecule tetracyanoquinodimethane (TCNQ) . Besides, the association and dissociation of the host–guest complex could be efficiently controlled by acid/base, anions, redox and photoacid, which provided an opportunity for us to develop stimuli‐responsive molecular switches and machines . In this regard, multiple stimuli‐responsive molecular machines based on helic[6]arenes remain unexplored.…”

Section: Introductionmentioning

confidence: 99%

A Triply Operable Molecular Switch: Anion‐, Acid/Base‐ and Solvent‐Responsive [2]Rotaxane

et al. 2019

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A 2,6‐helic[6]arene‐based bistable [2]rotaxane has been designed and synthesized, which incorporates protonated tertiary ammonium salt as a reversible control unit and hexamethylene chain as a second binding site. In particular, it was found that [2]rotaxane could perform as a triply operable molecular switch through addition and removal of fluoride ions (TBAF/NaBArF), protonation and deprotonation of tertiary amine (HBArF/DBU), and altering the solvent polarity. It represents the first triply operable molecular switch based on helic[6]arenes.

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“…Novel macrocyclic arenes have been reported successively in recent years to enrich the macrocyclic arene library [17]. Although the macrocyclic arene's recognition ability towards ammonium salts have been well studied [18][19][20][21][22], their enantioselective recognition towards ammonium salts, and especially those bioactive ammonium salts, have been rarely reported [23].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Chiral Helic[1]triptycene[3]arenes and Their Enantioselective Recognition towards Chiral Guests Containing Aminoindan Groups

Han

Chen

2021

Molecules

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Starting from the enantiopure precursors, a pair of chiral macrocyclic arenes named helic[1]triptycene[3]arenes were conveniently synthesized. The circular dichroism (CD) spectra of the enantiomeric macrocyclic arenes exhibited mirror images, and the X-ray single crystal structures confirmed their absolute conformations as well. Moreover, the macrocyclic arenes showed strong complexation with secondary ammonium and primary ammonium salts containing aminoindan groups. In particular, the chiral macrocyclic arenes exhibited enantioselective recognition ability towards the chiral secondary ammonium salts containing aminoindan groups with an enantioselective ratio up to 3.89.

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Complexation Between (O‐Methyl)₆‐2,6‐Helic[6]arene and Tertiary Ammonium Salts: Acid/Base‐ or Chloride‐Ion‐Responsive Host–Guest Systems and Synthesis of [2]Rotaxane

Cited by 16 publications

References 83 publications

Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes

Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes

A Triply Operable Molecular Switch: Anion‐, Acid/Base‐ and Solvent‐Responsive [2]Rotaxane

Synthesis of Chiral Helic[1]triptycene[3]arenes and Their Enantioselective Recognition towards Chiral Guests Containing Aminoindan Groups

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Complexation Between (O‐Methyl)6‐2,6‐Helic[6]arene and Tertiary Ammonium Salts: Acid/Base‐ or Chloride‐Ion‐Responsive Host–Guest Systems and Synthesis of [2]Rotaxane

Cited by 16 publications

References 83 publications

Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes

Triptycene-Derived Macrocyclic Arenes: From Calixarenes to Helicarenes

A Triply Operable Molecular Switch: Anion‐, Acid/Base‐ and Solvent‐Responsive [2]Rotaxane

Synthesis of Chiral Helic[1]triptycene[3]arenes and Their Enantioselective Recognition towards Chiral Guests Containing Aminoindan Groups

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Complexation Between (O‐Methyl)₆‐2,6‐Helic[6]arene and Tertiary Ammonium Salts: Acid/Base‐ or Chloride‐Ion‐Responsive Host–Guest Systems and Synthesis of [2]Rotaxane