Efficient 3D charge transport in planar triazatruxene-based dumbbell-shaped molecules forming a bridged columnar phase

Jing, Jiang; Heinrich, Benoît; Prel, Alexis; Steveler, Émilie; Han, Tianyan; Bulut, İbrahim; Méry, Stéphane; Leroy, Y.; Leclerc, Nicolas; Lévêque, P.; Rosenthal, Martin; Ivanov, Dimitri A.; Heiser, T.

doi:10.1039/d1ta06300f

Cited by 10 publications

(9 citation statements)

References 44 publications

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“…Also, the contribution of intra-grain defects acting as non-radiative recombination centers must be weak in order to allow the lifetime to exceed the reference value in solution [23][24][25] . The latter result is surprising, since the enhanced intermolecular coupling in the crystals, as revealed by high charge carrier mobility [14] , does not translate into additional non-radiative pathways but rather the opposite. This behavior may be a consequence of the fact that the polar environment in the crystals could differ considerably from that in the solution.…”

Section: Fig 2e and 2fmentioning

confidence: 96%

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Impact of the crystalline order on the exciton diffusion length in organic thin films of donor-acceptor-donor molecules based on triazatruxene units

Jiang

Steveler

Leclerc

et al. 2022

Organic Electronics and Photonics: Fundamentals and Devices III

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Organic semiconductor materials such as planar conjugated small molecules are of great interest to the photovoltaic community. In thin films, the exciton and charge carrier dynamics, which are crucial to photovoltaic device operation, depend in a non-trivial way on the organic molecular structure and on the molecular organization in the solid state. Recently, the exciton diffusion has been found to strongly depend on the crystalline order of the organic thin films. This work presents the study of the exciton lifetime in an innovative class of molecular semiconductors able to present different crystalline order. This family of molecules has a "dumbbell-shaped" structure based on triazatruxene units that act as a π-stacking platform. Such molecules with different side-chains have been found to self-assemble into various crystalline and liquid crystalline phases. We have studied the steady-state photoluminescence and the exciton lifetime for several triazatruxene-based derivatives with different side-chains, in solution and in thin films for different solid state phases. In solution, the fluorescence lifetime corresponds to the reference value that can be obtained without intermolecular interaction. In thin films, we measured the exciton lifetime for different molecular structures in order to correlate the exciton dynamics with the molecular stacking. The results reveal a significant increase in the exciton lifetime with the enhancement of the structural order.

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Section: Fig 2e and 2fmentioning

confidence: 96%

“…1). Such molecules have been found to self-assemble into various solid-state phases, including liquid crystal mesophases and more ordered purely crystalline phases, under certain post-deposition treatments [12,14] .…”

Section: Introductionmentioning

confidence: 99%

Impact of the crystalline order on the exciton diffusion length in organic thin films of donor-acceptor-donor molecules based on triazatruxene units

Jiang

Steveler

Leclerc

et al. 2022

Organic Electronics and Photonics: Fundamentals and Devices III

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“…Molecules 2022, 27, x FOR PEER REVIEW 2 of 14 a number of peripheral flexible chains to this molecule, it is possible to induce in this heptacyclic platform columnar mesomorphism giving rise to liquid crystalline materials that exhibit excellent hole mobilities values and can be easily processed from solution or melt [17][18][19]. Interestingly, mesomorphism can also be induced in this core by means of electronic factors.…”

Section: Synthesis and Electronic Propertiesmentioning

confidence: 99%

“…In addition, the triindole core, has been identified as an excellent aromatic core in the construction of high mobility p -type semiconducting discotic liquid crystals. By attaching a number of peripheral flexible chains to this molecule, it is possible to induce in this heptacyclic platform columnar mesomorphism giving rise to liquid crystalline materials that exhibit excellent hole mobilities values and can be easily processed from solution or melt [ 17 , 18 , 19 ]. Interestingly, mesomorphism can also be induced in this core by means of electronic factors.…”

Section: Introductionmentioning

confidence: 99%

Functionalized Crystalline N-Trimethyltriindoles: Counterintuitive Influence of Peripheral Substituents on Their Semiconducting Properties

et al. 2022

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Three crystalline N-trimethyltriindoles endowed with different functionalities at 3, 8 and 13 positions (either unsubstituted or with three methoxy or three acetyl groups attached) are investigated, and clear correlations between the electronic nature of the substituents and their solid-state organization, electronic properties and semiconductor behavior are established. The three compounds give rise to similar columnar hexagonal crystalline structures; however, the insertion of electron-donor methoxy groups results in slightly shorter stacking distances when compared with the unsubstituted derivative, whereas the insertion of electron-withdrawing acetyl groups lowers the crystallinity of the system. Functionalization significantly affects hole mobilities with the triacetyl derivative showing the lowest mobility within the series in agreement with the lower degree of order. However, attaching three methoxy groups also results in lower hole mobility values in the OFETs (0.022 vs. 0.0014 cm2 V−1 s−1) in spite of the shorter stacking distances. This counterintuitive behavior has been explained with the help of DFT calculations performed to rationalize the interplay between the intramolecular and intermolecular properties, which point to lower transfer integrals in the trimethoxy derivative due to the HOMO wave function extension over the peripheral methoxy groups. The results of this study provide useful insights into how peripheral substituents influence the fundamental charge transport parameters of chemically modified triindole platforms of fundamental importance to design new derivatives with improved semiconducting performance.

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“…As the electron withdrawing unit, we selected a thieno [3,4-c]pyrrole-4,6-dione (TPD) derivative. [36][37][38][39][40] TPD has the advantage to carry a long side-chain, which promotes solubility and lamellar selfassembly. In addition, TPD contains two different chemical sites that are prone to involve weak bonds with halogen atoms, i.e., the sulfur atom and the ketone group (highlighted in red in Figure 1).…”

Section: Research Articlementioning

confidence: 99%

How Halogenation Impacts the Polymer Backbone Conformation: Learning from Combination of Solid‐State MAS NMR and X‐Ray Scattering

Olla

Jabbour

Labiod

et al. 2022

Adv Funct Materials

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Over the past decade, halogenated semiconducting polymers have attracted considerable interest due to their outstanding optoelectronic properties. Thus, in most of today's organic photovoltaic devices benchmark organic semiconductors are halogenated materials, either electron donor polymers or non‐fullerene acceptor (NFA) small molecules. However, the nature and position of the substituted halogen atoms in halogenated semiconducting polymers impact, through self‐assembly modification, their optoelectronic properties in a way that is difficult to predict. Yet, the solid‐state self‐assembling of these materials has been shown to be a key parameter toward high charge transport properties and photovoltaic efficiencies. In this context, there is still a need to develop analytical methods that will enable an atomic‐scale structural characterization of these materials as a function of the halogenation. In this study, the solid‐state nuclear magnetic resonance (NMR) under magic angle spinning (MAS) is explored as a tool to investigate the local structure and supramolecular organization of a series of conjugated polymers, specially designed for this study. Through a comprehensive study using complementary techniques, including MAS–NMR, small and wide‐angle X‐ray scattering, and molecular modeling investigations, the molecular conformation of these polymers in relation to their chemical composition, is successfully determined.

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Efficient 3D charge transport in planar triazatruxene-based dumbbell-shaped molecules forming a bridged columnar phase

Abstract: Planar conjugated molecular backbones are essential for achieving high charge carrier mobilities along molecular -stacking directions but are often concomitant with poor charge transport in other directions. This is particularly...

Cited by 10 publications

References 44 publications

Impact of the crystalline order on the exciton diffusion length in organic thin films of donor-acceptor-donor molecules based on triazatruxene units

Impact of the crystalline order on the exciton diffusion length in organic thin films of donor-acceptor-donor molecules based on triazatruxene units

Functionalized Crystalline N-Trimethyltriindoles: Counterintuitive Influence of Peripheral Substituents on Their Semiconducting Properties

How Halogenation Impacts the Polymer Backbone Conformation: Learning from Combination of Solid‐State MAS NMR and X‐Ray Scattering

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