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Chair Conformation of Cyclohexane02:02

Chair Conformation of Cyclohexane

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The chair conformation is the most stable form of cyclohexane due to the absence of angle and torsional strain. The absence of angle strain is a result of cyclohexane’s bond angle being very close to the ideal tetrahedral bond angle of 109.5° in its chair conformer. Similarly, the torsional strain is also absent owing to the perfectly staggered arrangement of bonds.
The hydrogen atoms linked to carbons are arranged in two different axial and equatorial orientations to achieve this...
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Conformations of Cyclohexane02:11

Conformations of Cyclohexane

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Cyclohexane does not exist in a planar form due to the high angle and torsional strain it would experience in the planar structure. Instead, it adopts non-planar chair and boat conformations.
The chair form is the most stable and derives its name from its resemblance to the “easy chair.” In the chair conformation, two carbon atoms are arranged out-of-plane — one above and one below, minimizing the torsional strain. In the chair form, the bond angle is very close to the ideal...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)

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Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
3.0K
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

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Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

4.1K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
4.1K
Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

2.4K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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Recent advances in higher order rotaxane architectures.

He-Ye Zhou1, Qian-Shou Zong2, Ying Han3

  • 1Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. cchen@iccas.ac.cn hanying463@iccas.ac.cn and University of Chinese Academy of Sciences, Beijing 100049, China.

Chemical Communications (Cambridge, England)
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Summary

Synthesizing complex, higher order rotaxanes remains challenging but offers exciting applications in molecular machines. Recent advances focus on well-defined structures and stimuli-responsive molecular motion.

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Area of Science:

  • Supramolecular Chemistry
  • Materials Science

Background:

  • Archetypal [2]rotaxanes are well-established, but higher order rotaxanes present significant synthetic hurdles.
  • Higher order rotaxanes feature multiple interlocked molecular components, enabling complex architectures.

Purpose of the Study:

  • To review recent advancements in the synthesis of higher order rotaxanes.
  • To highlight diverse rotaxane architectures and their corresponding synthetic methodologies.
  • To discuss the stimuli-responsive molecular motion within these complex interlocked systems.

Main Methods:

  • Focus on template-directed synthesis strategies.
  • Description of various higher order rotaxane architectures.
  • Analysis of synthetic approaches for constructing complex rotaxanes.

Main Results:

  • Progress in achieving well-defined higher order rotaxane structures.
  • Demonstration of diverse synthetic routes for complex rotaxanes.
  • Exploration of stimuli-responsive behaviors in advanced rotaxane systems.

Conclusions:

  • Higher order rotaxanes are increasingly accessible through refined synthetic techniques.
  • These complex molecules are crucial for developing sophisticated artificial molecular machines.
  • Future research will likely focus on enhancing the complexity and functionality of rotaxane-based systems.