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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

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Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
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Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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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...
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Pericyclic Reactions: Introduction01:17

Pericyclic Reactions: Introduction

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Pericyclic reactions are organic reactions that occur via a concerted mechanism without generating any intermediates. The reactions proceed through the movement of electrons in a closed loop to form a cyclic transition state, where rearrangement of the σ and π bonds yields specific products.
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Thermal Electrocyclic Reactions: Stereochemistry01:17

Thermal Electrocyclic Reactions: Stereochemistry

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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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Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives
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Vapochemically and mechanochemically reversible polymerization/depolymerization of S-Fe-Cu carbonyl clusters.

Chien-Nan Lin1, Wei-Ting Jhu, Minghuey Shieh

  • 1Department of Chemistry, National Taiwan Normal University, 88, Sec. 4, Tingchow Road, Taipei 11677, Taiwan, Republic of China. mshieh@ntnu.edu.tw.

Chemical Communications (Cambridge, England)
|December 11, 2013
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Summary
This summary is machine-generated.

Researchers demonstrated a reversible solid-state transformation between a cluster and a polymer. The resulting polymer exhibits semiconducting properties with a 1.69 eV energy gap, showing potential for electronic applications.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Solid-State Chemistry

Background:

  • Metal-organic clusters and polymers are of interest for their unique properties.
  • Solid-state transformations offer pathways to novel materials with tunable characteristics.

Purpose of the Study:

  • To demonstrate a reversible solid-state transformation between a specific SFe3Cu2-based cluster and its 1D polymer.
  • To investigate the properties of the resulting polymer.

Main Methods:

  • Vapochemical and mechanochemical techniques were employed for the solid-state transformation.
  • Characterization of the cluster and polymer structures.
  • Measurement of the polymer's semiconducting properties, including energy gap determination.

Main Results:

  • A reversible transformation between the SFe3Cu2-based cluster [{(μ3-S)Fe3(CO)9}Cu2(dppe)] (2) and its 1D polymer [{(μ4-S)Fe3(CO)9}Cu2(dppe)(MeCN)2]n (3) was successfully achieved.
  • The 1D polymer (3) exhibited semiconducting behavior.
  • The energy gap of the polymer was determined to be 1.69 eV.

Conclusions:

  • The study successfully demonstrated a reversible vapochemical and mechanochemical solid-state transformation in an SFe3Cu2-based system.
  • The resulting 1D polymer possesses semiconducting properties, indicating potential applications in electronic materials.