A spectroscopic assessment of static and dynamic disorder in a film of a polythiophene with a planarized backbone

Schötz, Konstantin; Panzer, Fabian; Sommer, Michael; Bässler, Heinz; Köhler, Anna

doi:10.1039/d3mh01262j

Cited by 3 publications

(3 citation statements)

References 56 publications

(78 reference statements)

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“…Like the 1- E films, the 3a- E films appear amorphous after spin coating and become well-ordered J-aggregates after thermal annealing with the lowest energy peak for as-spun films 13 nm red-shifted relative to the solution absorbance and 31 nm red-shifted for annealed films. The 3a- E PL intensity increases 10-fold after annealing and the full width at half maximum (FWHM) narrows from 0.30 to 0.15 eV indicating a reduction in the static energetic disorder present in the films and crystallization-induced emission enhancement (CIEE) . The synergy of planarity and J-aggregation in the solid-state is known to be propitious for achieving aggregation-induced emission enhancement (AIEE), which is intrinsic to the E isomer for compounds 1 and 3a and is favorable for developing luminescent organic materials.…”

Section: Resultsmentioning

confidence: 99%

Dicyanorhodanine-Pyrrole Conjugates for Visible Light-Driven Quantitative Photoswitching in Solution and the Solid State

Das,

Grinalds,

Ghiviriga

et al. 2024

J. Am. Chem. Soc.

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Small molecule photoswitches capable of toggling between two distinct molecular states in response to light are versatile tools to monitor biological processes, control photochemistry, and design smart materials. In this work, six novel dicyanorhodanine-based pyrrole-containing photoswitches are reported. The molecular design avails both the Z and E isomers from synthesis, where each can be isolated using chromatographic techniques. Inter-and intramolecular hydrogen bonding (Hbonding) interactions available to the E and Z isomers, respectively, uniquely impart thermal stability to each isomer over long time periods. Photoisomerization could be assessed by solution NMR and UV−vis spectroscopic techniques along with complementary ground-and excited-state computational studies, which show good agreement. Quantitative E → Z isomerization occurs upon 523 nm irradiation of the parent compound (where R = H) in solution, whereas Z → E isomerization using 404 nm irradiation offers a photostationary state (PSS) ratio of 84/16 (E/Z). Extending the πconjugation of the pyrrole unit (where R = p-C 6 H 4 −OMe) pushes the maximum absorption to the yellow-orange region of the visible spectrum and allows bidirectional quantitative isomerization with 404 and 595 nm excitation. Comparator molecules have been prepared to report how the presence or absence of H-bonding affects the photoswitching behavior. Finally, studies of the photoswitches in neat films and photoinactive polymer matrices reveal distinctive structural and optical properties of the Z and E isomers and ultimately afford reversible photoswitching to spectrally unique PSSs using visible light sources including the Sun.

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Section: Resultsmentioning

confidence: 99%

Dicyanorhodanine-Pyrrole Conjugates for Visible Light-Driven Quantitative Photoswitching in Solution and the Solid State

Das,

Grinalds,

Ghiviriga

et al. 2024

J. Am. Chem. Soc.

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“…[41,42] The widths of the E 00 distributions reflect static disorder, resulting from a chain-to-chain variation of transition energies. [56] It therefore quantifies the variation of conjugation length and dielectric environment from chain to chain. For the fully hexylated compound P100, the narrow distribution of E 00 thus implies a lower torsional disorder.…”

Section: Resultsmentioning

confidence: 99%

“…[12,45] We found that the polythiophene with short side chains features a highly non-planar, twisted backbone geometry; the torsional disorder (i. e., the variation of dihedral angles) along the backbone, however, is rather small. In contrast, the bulky-substituted polythiophene possesses a highly planar backbone, [56] but the torsional disorder is significantly larger compared to the non-planar thiophene (the dihedral angle is widely distributed along each backbone). We could ascribe this difference to distinct non-covalent interactions between the thiophene backbones and the different side groups.…”

Section: Resultsmentioning

confidence: 99%

Hexylation Stabilises Twisted Backbone Configurations in the Prototypical Low‐Bandgap Copolymer PCDTBT

Stäter,

Woering,

Lombeck

et al. 2024

ChemPhysChem

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Conjugated donor‐acceptor copolymers hold great potential as materials for high‐performance organic photovoltaics, organic transistors and thermoelectric devices. Their low optical bandgap is achieved by alternation of donor and acceptor moieties along the polymer chain, leading to a pronounced charge‐transfer character of electronic excitations. However, the influence of appended side chains and of chemical defects of the backbone on their photophysical and conformational properties remains largely unexplored on the level of individual chains. Here, we employ room temperature single‐molecule photoluminescence spectroscopy on four compounds based on the prototypical copolymer PCDTBT with systematically changed chemical structure. Our results show that an increasing density of statistically added hexyl chains to the TBT comonomer distorts the molecular conformation, likely through the increase of average dihedral angles along the backbone. We find that, although the conformation becomes more twisted with high hexyl density, the side chains appear to stabilize the backbone in this twisted conformation. In addition, we demonstrate that homocoupling defects along the backbone barely influence the PL spectra of single chains, and thus intrachain electronic properties.

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Polythiophene/graphene oxide thin films: optical properties

Martínez,

Retana,

Gómez

2024

DJNB

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Thin films of polythiophene/graphene oxide (PTh/GO) were prepared using chronoamperometry. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (FESEM), UV-Vis spectroscopy, and photoluminescence spectroscopy (PL) were used for characterization purposes. PTh and PTh/GO thin films were achieved through chronoamperometry at a constant anodic potential of +1.9 V vs. Ag/AgCl. The PTh/GO thin films exhibited visible light absorption. The thicknesses of the thin films were approximately 2.42 µm.

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A spectroscopic assessment of static and dynamic disorder in a film of a polythiophene with a planarized backbone

Abstract: The optoelectronic performance of organic semiconductor devices is related to the static and dynamic disorder in the film. The disorder can be assessed by considering the linewidth of its optical...

Cited by 3 publications

References 56 publications

Dicyanorhodanine-Pyrrole Conjugates for Visible Light-Driven Quantitative Photoswitching in Solution and the Solid State

Dicyanorhodanine-Pyrrole Conjugates for Visible Light-Driven Quantitative Photoswitching in Solution and the Solid State

Hexylation Stabilises Twisted Backbone Configurations in the Prototypical Low‐Bandgap Copolymer PCDTBT

Polythiophene/graphene oxide thin films: optical properties

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