Joint experimental and theoretical study of the poly(styryl sodium) and poly(α-methylstyryl sodium) polymerization/depolymerization

文献情報

出版日 2001-09-20

DOI 10.1039/B105389M

インパクトファクター 3.676

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要旨

Ab initio 6-31G* optimization of a fragment of poly(styryl sodium) and poly(α-methylstyryl sodium) composed of two monomer units in cis-configuration gives rise to low energies of the triplet state. The novel mechanism of living polymer depolymerization is proposed, involving thermal excitation into the low-lying triplet state of charge transfer character followed by bond breaking. In the elementary stage of depolymerization the electronic excitation of the reaction structure in the cis-configuration is accompanied by a minor (∽0.5 Å) displacement of the Na+ cation between the terminal and the penultimate monomer units. The direct reaction of adding the styrene molecule to the terminal unit of a living polymer was also considered. The reversible reaction of polymerization/depolymerization of poly(α-methylstyryl sodium) in THF was studied experimentally. A semi-empirical AM1 method was used to estimate the geometry and the charge distribution.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.