Modular Synthesis of Improbable Rotaxanes with All‐Benzene Scaffolds

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 26, 2024

"Improbable" rotaxanes consisting of interlocked conjugated components represent non-trivial synthetic targets, not to mention those with all-benzene scaffolds. Herein, a modular strategy has been established using an isolable azo-linked pre-rotaxane as the core module, in which azo group functions tracelessly removable template direct mechanical bond formations. Through versatile connections and other customizable modules, [2]- [3]rotaxanes derived from scaffolds have accomplished, demonstrating utility potential design for supramolecules.

Language: Английский

---

Supramolecular and molecular capsules, cages and containers

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(21), P. 10380 - 10408

Published: Jan. 1, 2024

Stemming from early seminal notions of molecular recognition and encapsulation, three-dimensional, cavity-containing capsular compounds assemblies have attracted intense interest due to the ability modulate chemical physical properties species encapsulated within these confined spaces compared bulk environments. With such a diverse range covalent motifs non-covalent (supramolecular) interactions available assemble building blocks, an incredibly wide-range capsular-type architectures been developed. Furthermore, synthetic tunability internal environments gives chemists opportunity engineer systems for uses in sensing, sequestration, catalysis transport molecules, just name few. In this tutorial review, overview is provided into design principles, synthesis, characterisation, structural facets coordination cages, porous organic supramolecular capsules, foldamers mechanically interlocked molecules. Using recent examples, advantages limitations each system are explored, highlighting their application various tasks functions.

Language: Английский

---

Active template synthesis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The active template synthesis of rotaxanes, catenanes and knots exploits the dual ability metals, or particular arrangements functional groups, to serve as both a catalyst assemble covalently capture interlocked molecules.

Language: Английский

---

Molecular entanglement can strongly increase basicity

Communications Chemistry, Journal Year: 2024, Volume and Issue: 7(1)

Published: May 28, 2024

Brønsted basicity is a fundamental chemical property featured by several kinds of inorganic and organic compounds. In this Review, we treat particularly high resulting from the mechanical entanglement involving two or more molecular subunits in catenanes rotaxanes. Such allows number basic sites to be close proximity with each other, highly increasing proton affinity comparison corresponding, non-entangled counterparts up obtain superbases, properly defined as mechanically interlocked superbases. following pages, development kind superbases will described historical perusal, starting initial, serendipitous findings most recent reports where strong entangled units object rational design.

Language: Английский

---

Skeletal Editing of Mechanically Interlocked Molecules: Nitrogen Atom Deletion from Crown Ether-Dibenzylammonium Rotaxanes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29496 - 29502

Published: Oct. 21, 2024

Removing the nitrogen atom from secondary amines while simultaneously linking remaining fragments is a powerful form of late-stage skeletal editing. Here, we report its use for deletion dibenzylammonium template used to assemble crown ether rotaxanes. The reaction uses an anomeric amide that activates generate carbon-carbon bond replaces amine nitrogen. Despite potential dethreading intermediate diradical pair, was successfully deleted series rotaxane axles as long macrocycle could access coconformations did not inhibit group. skeletally edited interlocked molecules were obtained directly parent ether-dibenzylammonium rotaxanes in modest yields (23-36%) and characterized by NMR spectroscopy, mass spectrometry, X-ray crystallography. One shows network weak CH···O hydrogen bonds between benzylic methylene groups axle solid state, place ether-ammonium binding motif parent, unedited, rotaxane.

Language: Английский

---

Modular Synthesis of Improbable Rotaxanes with All‐Benzene Scaffolds

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(18)

Published: Feb. 26, 2024

Abstract “Improbable” rotaxanes consisting of interlocked conjugated components represent non‐trivial synthetic targets, not to mention those with all‐benzene scaffolds. Herein, a modular strategy has been established using an isolable azo‐linked pre‐rotaxane as the core module, in which azo group functions tracelessly removable template direct mechanical bond formations. Through versatile connections and other customizable modules, [2]‐ [3]rotaxanes derived from scaffolds have accomplished, demonstrating utility potential design for supramolecules.

Language: Английский

---

Simultaneous Hydrogenation of an Insulated Diarylacetylene Dimer Incorporated as Axle Molecules in a Cyclodextrin‐Based [c2]Daisy Chain Rotaxane

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 21, 2024

The [c2]daisy chain rotaxane is an attractive interlocked molecule for the development of functional materials because its unique mechanical properties that respond to various external stimuli, resulting in extension and contraction motions along molecular axis. synthesis several 'impossible' [2]rotaxanes do not exhibit obvious binding motifs between their axle wheel moieties has been achieved through further chemical modification within pre-prepared [2]rotaxanes. However, no synthesized using similar strategies until now. In this study, we investigated hydrogenation diarylacetylene a permethylated α-cyclodextrin (PM α-CD)-based Pd/C or Pd/CaCO

Language: Английский

---