Cover Feature: Analysis of Conjugated Polymers Conductivity by in situ Electrochemical‐Conductance Method (ChemElectroChem 16/2019)

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, and are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis of n-type π-conjugated polymers. Herein we provide an experimental and computational investigation of the mechanism of this photopolymerization. Spectroscopic studies performed in situ and after quenching reveal that the propagating species is a radical anion with halide end groups. DFT calculations for model oligomers suggest a Mg-templated SRN1-type coupling, in which Grignard monomer coordination to the radical anion chain avoids the formation of free sp2 radicals and enables C–C bond formation with very low barriers. We find that light plays an unusual role in the reaction, photoexciting the radical anion chain to shift electron density to the termini and thus favor productive monomer binding.

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One-step process for the preparation of fast-response soft actuators based on electrospun hybrid hydrogel nanofibers obtained by reactive electrospinning with in situ synthesis of conjugated polymers

Polymer ◽

10.1016/j.polymer.2020.122590 ◽

2020 ◽

Vol 200 ◽

pp. 122590 ◽

Cited By ~ 1

Author(s):

Diego Oliveira Miranda ◽

Matheus Figueiredo Dorneles ◽

Rodrigo Lambert Oréfice

Keyword(s):

Conjugated Polymers ◽

Fast Response ◽

In Situ Synthesis ◽

Hybrid Hydrogel ◽

Step Process ◽

One Step ◽

Soft Actuators

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A solid reaction towards in situ hybridization of carbon dots and conjugated polymers for enhanced light absorption and conversion

Chemical Communications ◽

10.1039/c7cc05526a ◽

2017 ◽

Vol 53 (68) ◽

pp. 9426-9429 ◽

Cited By ~ 13

Author(s):

Shengliang Hu ◽

Yufeng Zhou ◽

Chaorui Xue ◽

Jinlong Yang ◽

Qing Chang

Keyword(s):

In Situ Hybridization ◽

Energy Level ◽

Conjugated Polymers ◽

Carbon Dots ◽

Level Structure ◽

Electronic Energy ◽

Solid Reaction ◽

Energy Level Structure ◽

Electronic Energy Level

The incorporation of carbon dots into poly(diphenylbutadiyne) nanostructures induces the change of the electronic energy level structure and enhances photocatalytic performances.

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Preparation of defect-free nanocaterpillars via in situ nanoparticlisation of a well-defined polyacetylene block copolymer

RSC Advances ◽

10.1039/c4ra10325d ◽

2014 ◽

Vol 4 (90) ◽

pp. 49180-49185 ◽

Cited By ~ 13

Author(s):

Ki-Young Yoon ◽

In-Hwan Lee ◽

Tae-Lim Choi

Keyword(s):

Block Copolymer ◽

Conjugated Polymers ◽

Diblock Copolymers ◽

One Pot

We report one-pot preparation of defect-free nanocaterpillars via in situ nanoparticlisation of conjugated polymers which were prepared by ROMP to produce diblock copolymers containing polyacetylene.

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Molecular-Level Processing of Conjugated Polymers. 2. Layer-by-Layer Manipulation of In-Situ Polymerized p-Type Doped Conducting Polymers

Macromolecules ◽

10.1021/ma00125a013 ◽

1995 ◽

Vol 28 (21) ◽

pp. 7115-7120 ◽

Cited By ~ 112

Author(s):

A. C. Fou ◽

M. F. Rubner

Keyword(s):

Conducting Polymers ◽

Conjugated Polymers ◽

Molecular Level ◽

Layer By Layer ◽

P Type

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Электрохимический контроль электронной проводимости тонких пленок металлоорганических полимеров

Письма в журнал технической физики ◽

10.21883/pjtf.2021.16.51329.18830 ◽

2021 ◽

Vol 47 (16) ◽

pp. 43

Author(s):

М.П. Карушев ◽

А.М. Тимонов

Keyword(s):

Thin Films ◽

Electrical Resistance ◽

Doping Level ◽

Macrocyclic Complex ◽

Polymer Complexes ◽

Electrochemical Doping ◽

Conductance Method

The dependence of the conductivity in thin films of polymer complexes of nickel with N4 ligands with macrocyclic and chelate structure on the doping level has been studied by the electrochemical in-situ conductance method. The electrochemical conductivity window of polymers depends on the structure of the monomers and approached 1.2 V for the macrocyclic complex. Electrochemical doping changes the electrical resistance of the investigated materials by 4 orders of magnitude

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Charge-Transfer Intermediates in the Electrochemical Doping Mechanism of Conjugated Polymers

10.26434/chemrxiv.13063916 ◽

2020 ◽

Author(s):

Ilaria Bargigia ◽

Lisa R. Savagian ◽

Anna M. Österholm ◽

John R. Reynolds ◽

Carlos Silva

Keyword(s):

Charge Transfer ◽

Conjugated Polymers ◽

Transient Absorption ◽

Electronic Conductivity ◽

Environmental Parameters ◽

Local Environment ◽

Precursor State ◽

Electrochemical Doping ◽

Heterogeneous Polymer

In this work, we address the nature of electrochemically induced charged states in conjugated polymers, their evolution as a function of electrochemical potential, and their coupling to their local environment by means of transient absorption and Raman spectroscopies synergistically performed in situ throughout the electrochemical doping process. In particular, we investigate the fundamental mechanism of electrochemical doping in an oligoether-functionalized 3,4-propylenedioxythiophene (ProDOT) copolymer. The changes embedded in both linear and transient absorption features allow us to identify a precursor electronic state with charge-transfer (CT) character that precedes polaron formation and bulk electronic conductivity. This state is shown to contribute to the ultrafast quenching of both neutral molecular excitations and polarons. Raman spectra relate the electronic transition of this precursor state predominantly to the Cβ -Cβ stretching mode of the thiophene heterocycle. We characterize the coupling of the CT-like state with primary excitons and electrochemically induced charge separated states, providing insight into the energetic landscape of a heterogeneous polymer-electrolyte system and demonstrate how such coupling depends on environmental parameters, such as polymer structure, electrolyte composition, and environmental polarity.

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