Impact of the Replacement of a Triphenylamine by a Diphenylmethylamine Unit on the Electrochemical Behavior of Pentaerythritol‐Based Push‐Pull Tetramers

Malacrida, Claudia; Habibi, Amir Hossein; Gámez‐Valenzuela, Sergio; Lenko, Illia; Marqués, Pablo Simón; Labrunie, Antoine; Grolleau, Jérémie; Navarrete, Juan T. López; Delgado, M. Carmen Ruiz; Cabanetos, Clément; Blanchard, Philippe; Ludwigs, Sabine

doi:10.1002/celc.201900565

Cited by 10 publications

(12 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We were interested in developing an independent method to assess N v of MB doped PDPP-3T. To obtain an estimate for the molar attenuation coefficient ε P2 of the hole polaron we chose to combine two established characterization methods, spectroelectrochemistry [30,[37][38][39] and chronoamperometry (Figure 3). [40][41][42] The electrochemical cell comprised a polymer film with a thickness of d ≈ 140 nm spin-cast onto an ITO/glass working electrode, a Pt wire counter electrode and a Ag wire pseudoreference electrode, which were submerged in an electrolyte solution of 0.1 M TBAPF 6 in acetonitrile (AcN; cf.…”

Section: (3 Of 8)mentioning

confidence: 99%

Chemical Doping of Conjugated Polymers with the Strong Oxidant Magic Blue

Hofmann

Kroon

Zokaei

et al. 2020

Adv Elect Materials

Self Cite

View full text Add to dashboard Cite

The opto-electronic as well as the mechanical properties of semiconducting polymers depend strongly on the charge-carrier density, which can be tuned chemically or electrochemically, a process which is referred to as doping. Hence, doping is a powerful tool to optimize the performance of organic electronic devices, such as transistors, solar cells and organic light-emitting diodes (OLEDs), [1,5] as well as of organic thermoelectric materials. [6][7][8] Further, in case of electrochemical transistors and light-emitting electrochemical cells, modulation of the charge-carrier density is essential to the operation of these devices. [9,10] One way to introduce charges is via redox doping, also referred to as molecular doping, which involves an electron transfer between the semiconducting polymer and a small molecule, the socalled redox dopant. In case of p-doping a positive energetic offset between the electron affinity (EA) of the small-molecular dopant and the ionization energy (IE) of the semiconducting polymer is advantageous, i.e., EA dopant > IE polymer . Depending on the relative position of the energy levels one or even two electrons can be transferred from the polymer backbone to a dopant molecule. [11] A broad variety of p-and n-type polymer-dopant couples have been studied. The most common p-type redox dopant is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), [12,13] which shows an electron affinity of EA ≈ 5.2 eV and readily oxidizes polymers such as poly(3-hexylthiophene) (P3HT; IE ≈ 5.1 eV) [14][15][16][17][18][19] and thiophene-thienothiophene copolymers (PBTTT; IE ≈ 5.2 eV). [20,21] Many other conjugated polymers such as, for example, high-mobility donor-acceptor polymers have an IE of more than 5.3 eV and can therefore not be doped with F4TCNQ. At the same time, doping of high mobility polymers is of special interest in the field of organic thermoelectrics, because the use of such polymers may allow to increase the thermoelectric power factor, which scales with the electrical conductivity and hence charge-carrier mobility. [22,23] There are only few examples of dopants with a high electron affinity including 1,3,4,5,7,8-hexafluoro-tetracyano-naphthoquinodimethane (F6TCNNQ) (EA ≈ 5.3 eV), [11,24] hexacyano-trimethylene-cyclopropane (EA ≈ 5.9 eV) [24] and its derivatives, [25] and molybdenum dithiolene complexes such as Mo(tfd-COCF 3 ) 3 Molecular doping of organic semiconductors is a powerful tool for the optimization of organic electronic devices and organic thermoelectric materials. However, there are few redox dopants that have a sufficiently high electron affinity to allow the doping of conjugated polymers with an ionization energy of more than 5.3 eV. Here, p-doping of a broad palette of conjugated polymers with high ionization energies is achieved by using the strong oxidant tris(4bromophenyl)ammoniumyl hexachloroantimonate (Magic Blue). In particular diketopyrrolopyrrole (DPP)-based copolymers reach a conductivity of up to 100 S cm −1 and a thermoelectric power factor of 10 µW m −...

show abstract

Section: (3 Of 8)mentioning

confidence: 99%

Chemical Doping of Conjugated Polymers with the Strong Oxidant Magic Blue

Hofmann

Kroon

Zokaei

et al. 2020

Adv Elect Materials

Self Cite

View full text Add to dashboard Cite

show abstract

“…[12][13][14][15] Electrochemical crosslinking is very versatile when conducting substrates are used, resulting even in multifunctional polymer architectures in the case of multifunctional monomers. [16][17][18][19] A relatively simple and reliable method to introduce new functional species in a given polymer film is click chemistry, which is a term describing a set of criteria for chemically versatile and efficient reactions, defined by Sharpless et al in 2001. [20] A typical click reaction is the copper catalyzed 1,3dipolar cycloaddition of azides and alkynes (CuAAC) to regioselectively give 1,4-triazole products.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Characterization of Redox Probes Confined in 3D Conducting Polymer Networks

Kuhlmann

Liu

Dirnberger

et al. 2021

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

In this manuscript we present a versatile platform for introducing functional redox species into tailor-made 3D redox polymer networks. Electrochemical characterization based on cyclic voltammetry is applied to verify the immobilization of the redox species within the conducting networks. Ultimately this strategy shall be extended to (photo)electrocatalytic applications which will profit from the conducting polymer matrix. Soluble precursor copolymers are synthesized via radical copolymerization of vinyltriphenylamine (VTPA) with chloromethylstyrene (CMS) in different ratios, whereas CMS is subsequently converted into azidomethylstyrene (AMS) to yield poly(VTPA-co-AMS) copolymers. Spin-coating of poly(VTPA-co-AMS) on gold electrodes yields thin films which are converted into stable polymer network structures by electrochemical crosslinking of the polymer chains via their pendant triphenylamine groups to yield N,N,N',N'-tetraphenylbenzidine (TPB) crosslinking points. Finally, the resulting redox-active, TPB-crosslinked films are functionalized with ethynylferrocene (EFc) as a representative redox probe using a click reaction. Main experimental tools are polarization modulation infrared reflection absorption spectroscopy and scan rate dependent cyclic voltammetry. Especially the latter proves the successful conversion and the immobilization of redox probes in the polymer matrix. The results are compared with the reference system of azideterminated self-assembled monolayers on gold substrates, allowing to distinguish between free and immobilized EFc species.

show abstract

“…Further, the charge screening ability and stabilization of the oxidation products in CH 3 CN does not lead to electrodeposition [22,30] . Examples of solvent influence on the radical‐cation reactivity towards dimerization can be found in the literature [22,31] …”

Section: Resultsmentioning

confidence: 99%

In Situ Electrochemical Investigations of Inherently Chiral 2,2′‐Biindole Architectures with Oligothiophene Terminals

et al. 2021

Self Cite

View full text Add to dashboard Cite

The synthesis and characterization of three new inherently chiral N,N′‐dipropyl‐3,3′‐diheteroaryl‐2,2′‐biindole monomers, nicknamed Ind2T4, Ind2T6 and Ind2Ph2T4, which differ in the number of thiophenes as terminals, are reported. In addition to a full monomer characterization, stable electroactive oligomeric films were obtained by electro‐oxidation upon cycling to potentials which activate the thiophene terminals. Cyclic voltammetry, UV‐Vis‐NIR spectroelectrochemistry and in situ conductance measurements show that oligomeric films of Ind2T6 present the best stability and electrochromic switching performance. Enantioselective tests with a chiral ferrocene amine clearly show the potential as chiral selectors for analytical and sensing purposes.

show abstract

Impact of the Replacement of a Triphenylamine by a Diphenylmethylamine Unit on the Electrochemical Behavior of Pentaerythritol‐Based Push‐Pull Tetramers

Cited by 10 publications

References 42 publications

Chemical Doping of Conjugated Polymers with the Strong Oxidant Magic Blue

Chemical Doping of Conjugated Polymers with the Strong Oxidant Magic Blue

Electrochemical Characterization of Redox Probes Confined in 3D Conducting Polymer Networks

In Situ Electrochemical Investigations of Inherently Chiral 2,2′‐Biindole Architectures with Oligothiophene Terminals

Contact Info

Product

Resources

About