Redox-controlled fluorescence modulation (electrofluorochromism) in triphenylamine derivatives

Quinton, Cassandre; Alain-Rizzo, Valérie; Dumas‐Verdes, Cécile; Miomandre, Fabien; Clavier, Gilles; Audebert, Pierre

doi:10.1039/c4ra02675f

Cited by 65 publications

(59 citation statements)

References 74 publications

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“…The SbF 6 − counterion accommodates the cavity created by the fluorenyl flanks next to the positively charged triphenylamine core with short N⋅⋅⋅F distance (2.88 Å). As with other bridged triphenylamines oxidation of 4 leads to a more rigid triphenylamine core. This structural situation is reflected by reduced bending angles of the peripheral fluorenyls in 4 .…”

Section: Figurementioning

confidence: 94%

“…Arylamines are ubiquitous in cutting‐edge materials and their applications are manifold ranging from benchmark hole‐transporting materials, such as spiro‐MeOTAD, efficient light emitters based on thermally activated delayed fluorescence, or donor components in push‐pull chromophores for photovoltaics . Aromatic amines are typically characterized by moderate to low oxidation potentials . Their corresponding radical cations — if isolable as salts — have shown merit as efficient organic oxidants .…”

Section: Figurementioning

confidence: 99%

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A Spherically Shielded Triphenylamine and Its Persistent Radical Cation

Schaub

Mekelburg

Dral

et al. 2020

Chemistry A European J

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This work reports the design and synthesis of a sterically protected triphenylamine scaffold which undergoes one‐electron oxidation to form an amine‐centered radical cation of remarkable stability. Several structural adjustments were made to tame the inherent reactivity of the radical cation. First, the parent propeller‐shaped triphenylamine was planarized with sterically demanding bridging units and, second, protecting groups were deployed to block the reactive positions. The efficiently shielded triphenylamine core can be reversibly oxidized at moderate potentials (+0.38 V, vs. Fc/Fc+ in CH2Cl2). Spectroelectrochemistry and chemical oxidation studies were employed to monitor the evolution of characteristic photophysical features. To obtain a better understanding of the impact of one‐electron oxidation on structural and electronic properties, joint experimental and computational studies were conducted, including X‐ray structural analysis, electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations. The sterically shielded radical cation combines various desirable attributes: A characteristic and unobstructed absorption in the visible region, high stability which enables storage for weeks without spectroscopically traceable degradation, and a reliable oxidation/re‐reduction process due to effective screening of the planarized triphenylamine core from its environment.

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Section: Figurementioning

confidence: 94%

Section: Figurementioning

confidence: 99%

A Spherically Shielded Triphenylamine and Its Persistent Radical Cation

Schaub

Mekelburg

Dral

et al. 2020

Chemistry A European J

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“…The two−step redox of P(TPACO) in above CV and DPV curves is assigned to the sequential conversion of TPA moiety to its cationic 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 11 radical (polaron) and dication (bipolaron) species. 6 The approximately symmetrical areas between the oxidation and reduction waves suggest a good reversibility of these redox reactions.…”

Section: Electrochemical Propertymentioning

confidence: 99%

Swift Electrofluorochromism of Donor–Acceptor Conjugated Polytriphenylamines

Sun

Liang

2016

ACS Appl. Mater. Interfaces

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Electrofluorochromic (EFC) materials, which exhibit electrochemically controllable fluorescence, hold great promise in optoelectronic devices and biological analysis. Here we design such donor-acceptor (D-A) conjugated polymers-P(TPACO) and P(TCEC)-that contain the same electron-rich and oxidizable polytriphenylamine (PTPA) as π-backbone, yet with different electron-deficient ketone and cyano units as pendant groups, respectively. They both exhibit solvatochromic effects due to intrinsic characteristics of intramolecular charge transfer (ICT). Compared to P(TPACO), P(TCEC) shows stronger ICT, which leads to higher electrochemical oxidation potential and lower ion diffusion coefficient. Moreover, both polymers present simultaneous electrochromic (EC) and EFC behaviors with multistate display and remarkably rapid fluorescence response. The response time of P(TPACO) is as short as 0.19 s, nearly 4-fold faster than that of P(TCEC) (0.92 s). Such rapid response is found to be determined by the ion diffusion coefficient which is associated with the ICT nature. Finally, the EFC display device based on P(TPACO) is successfully demonstrated, which shows green fluorescence ON/OFF switching upon applied potentials. This work has successfully demonstrated that swift EFCs can be achieved by rational modulation of the ICT effect in such D-A conjugated polymers.

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“…In this case, non‐radiative decay is important. In these compounds, the dissipation of electron energy is carried out by the rotation of the structural unit . Clearly, the presence of F atoms (the strongest polar atoms) leads to a more effective radiation deactivation of the excited state or a decrease in the rate of radiationless relaxation of the excited state for these modified substrates.…”

Section: Resultsmentioning

confidence: 99%

Surface Engineering of Organic Polymers by Photo‐induced Free Radical Coupling with p‐Dimethylaminophenyl Group as A Synthesis Block

et al. 2020

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This contribution presents a versatile strategy to transfer unactivated surface C–H bonds of polymeric substrates to C–R–F groups (R stands for a spacer and F stands for functional group) by UV light‐assisted surface free radical coupling. With p‐dimethylaminophenyl radical as a building block, various reactive groups, such as –CHO, –SH, –B(O)OH, –CN and –SO3−, are successfully grafted onto typical commercial polymer substrates including biaxially oriented polypropylene, polyethylene phthalate, ethylene tetrafluoroethylene copolymer and dimethyl silicone rubber. Fluorencence microscope images, X‐ray photoelectron spectroscopy, UV‐vis and fluorescence spectra support that the above functional groups are covalently bonded to the polymer substrates. The concentration of the reactive groups immobilized on the different substrates is in the order of 10−8 to 10−7 mmol mm−2 determined by UV‐vis spectrometry. In addition, as a proof‐of‐concept, the introduced functional groups are demonstrated by their special reactions, for example, –CHO reacting with –NH2 to synthesize Schiff base, –SH to detect silver ions, and the complexes of –C=N and Zn2+ to degrade Rhodamine B. The results indicate that one can fabricate an integrated molecular library on the surface of polymeric substrates at the molecular level by selecting the building blocks.

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Redox-controlled fluorescence modulation (electrofluorochromism) in triphenylamine derivatives

Abstract: The study of the chemical and electrochemical fluorescence switching properties of a family of substituted triphenylamine derivatives is reported.

Cited by 65 publications

References 74 publications

A Spherically Shielded Triphenylamine and Its Persistent Radical Cation

A Spherically Shielded Triphenylamine and Its Persistent Radical Cation

Swift Electrofluorochromism of Donor–Acceptor Conjugated Polytriphenylamines

Surface Engineering of Organic Polymers by Photo‐induced Free Radical Coupling with p‐Dimethylaminophenyl Group as A Synthesis Block

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