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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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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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Olefin Metathesis Polymerization: Overview01:13

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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.
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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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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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Formación de un polirotaxano basado en una plataforma de descobre cuya "cuerdas" y "perlas" están construidas a

Huiyeong Ju1, Jack K Clegg2, Ki-Min Park1

  • 1†Department of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju 660-701, S. Korea.

Journal of the American Chemical Society
|July 18, 2015
PubMed
Resumen

Los investigadores crearon un nuevo polirotaxano unidimensional utilizando componentes de cobre y un vinculante de piridilpiperazina. Esta estructura supramolecular cuenta con "perlas" autoenhebradas en una "corda" hecha de bloques de construcción idénticos.

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Área de la Ciencia:

  • Química de coordinación
  • Química supramolecular
  • Ciencias de los materiales

Sus antecedentes:

  • Los polirotaxanos son arquitecturas moleculares mecánicamente entrelazadas con aplicaciones potenciales en nanotecnología.
  • La síntesis de estructuras complejas de polirotaxano a menudo requiere procedimientos complejos en varios pasos.

Objetivo del estudio:

  • Informar de la primera síntesis de un polirotaxano unidimensional utilizando componentes idénticos tanto para la cuerda como para la perla.
  • Investigar el mecanismo de autoensamblaje impulsado por interacciones moleculares específicas.

Principales métodos:

  • Utilizó una plataforma de cobre [Cu2 ((L) 2 ((THF) 2)) y 1,4-bis ((4-piridil) piperazina (bpp) como bloques de construcción.
  • Se caracterizó la estructura de polirotaxano resultante utilizando las técnicas analíticas adecuadas.

Principales resultados:

  • Se ha sintetizado con éxito un polirotaxano unidimensional {[(1)
  • El polirotaxano presenta una cuerda en forma de escalera enredada por "perlas" rectangulares con dimensiones de 7,40 × 15,64 Å.
  • Identificó el apilamiento π-π como la principal fuerza impulsora del proceso de autoensamblaje.

Conclusiones:

  • Demostró un método fácil para construir polirotaxanos complejos a partir de un solo conjunto de componentes.
  • La complementariedad electrónica y estérica precisa entre los componentes de la cuerda y la perla es crucial para la formación exitosa de polirotaxano.
  • Propuso una vía plausible para el auto-ensamblaje de esta estructura supramolecular única.