Unraveling the unusual effect of fluorination on crystal packing in an organic semiconductor

Комиссарова, Екатерина А.; Dominskiy, Dmitry I.; Zhulanov, V. E.; Абашев, Г. Г.; Siddiqui, Afzal S.; Singh, Surya Prakash; Sosorev, Andrey Yu.; Paraschuk, Dmitry Yu.

doi:10.1039/c9cp05455c

Cited by 18 publications

(17 citation statements)

References 64 publications

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“…NDI-Chex and NDI-Hex molecules consist of rigid NDI cores and two flexible hexyl (NDI-Hex) or cyclohexyl (NDI-Chex) side chains (Figure 1). In line with earlier reports, [31,51,52] the frontier molecular orbitals, HOMO and LUMO, which are related to charge transport, are located at the NDI core (see Figure S2, Supporting Information), while terminal substituents are not involved in the π-conjugated system. The LUMO and HOMO patterns are very similar for NDI-Chex and NDI-Hex.…”

Section: Moleculessupporting

confidence: 91%

Non‐Local Electron‐Phonon Interaction in Naphthalene Diimide Derivatives, its Experimental Probe and Impact on Charge‐Carrier Mobility

Vener

Parashchuk

Kharlanov

et al. 2021

Adv Elect Materials

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Efficient operation of organic electronic devices requires high charge‐carrier mobilities in their active layers, but only several organic semiconductors show confirmed charge‐carrier mobilities exceeding that of amorphous silicon (≈1 cm2 V−1 s−1). Charge transport in high‐mobility organic semiconductor crystals is considerably hindered by non‐local electron‐phonon interaction (NLEPI) transforming dynamic disorder induced by low‐frequency (LF) vibrations into fluctuations of charge transfer integrals. In this work, using two crystals of naphthalene diimide derivatives as an example, LF vibrational modes that strongly modulate the charge transfer integrals are computationally revealed. The importance of the discussed LF modes for limiting the charge‐carrier mobility is justified by analyzing the effect of the dynamic disorder on the charge‐carrier dynamics, estimating the charge‐carrier mobility in the two crystals, and observing quite a good agreement of the latter with the experimental values. Finally, it is shown that the contribution of various modes to the NLEPI correlates with their experimental Raman intensities. As a result, it is suggested that LF Raman spectroscopy can be used for experimental study of NLEPI, which can help with screening organic semiconductors showing high charge‐carrier mobility and promote rational design of such materials.

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Section: Moleculessupporting

confidence: 91%

Non‐Local Electron‐Phonon Interaction in Naphthalene Diimide Derivatives, its Experimental Probe and Impact on Charge‐Carrier Mobility

Vener

Parashchuk

Kharlanov

et al. 2021

Adv Elect Materials

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“…However, most crystals with actual or potential practical application have little in common with the structures from the benchmark sets. Some examples include single-component crystals of larger, conformationally flexible molecules [10][11][12][13][14], fluoroorganic compounds [15,16], and multicomponent crystals [17][18][19], often with short (strong) [20,21] or ionic H-bonds [22]. The applicability of the methods tested against the benchmark sets for modeling the properties of non-model crystals (e.g., organic salts) is unclear.…”

Section: Introductionmentioning

confidence: 99%

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

et al. 2020

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Synthesis of multicomponent solid forms is an important method of modifying and fine-tuning the most critical physicochemical properties of drug compounds. The design of new multicomponent pharmaceutical materials requires reliable information about the supramolecular arrangement of molecules and detailed description of the intermolecular interactions in the crystal structure. It implies the use of a combination of different experimental and theoretical investigation methods. Organic salts present new challenges for those who develop theoretical approaches describing the structure, spectral properties, and lattice energy Elatt. These crystals consist of closed-shell organic ions interacting through relatively strong hydrogen bonds, which leads to Elatt > 200 kJ/mol. Some technical problems that a user of periodic (solid-state) density functional theory (DFT) programs encounters when calculating the properties of these crystals still remain unsolved, for example, the influence of cell parameter optimization on the Elatt value, wave numbers, relative intensity of Raman-active vibrations in the low-frequency region, etc. In this work, various properties of a new two-component carbendazim maleate crystal were experimentally investigated, and the applicability of different DFT functionals and empirical Grimme corrections to the description of the obtained structural and spectroscopic properties was tested. Based on this, practical recommendations were developed for further theoretical studies of multicomponent organic pharmaceutical crystals.

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“…7,8,16 Moreover, in exotic cases uorination induces the opposite crossover in the crystal structure-from the p-stacking to herringbone motif. [17][18][19] Thus, it is important to predict whether certain changes in the molecular (chemical) structure will be favorable or detrimental for optoelectronic applications. This prediction could be based on general "molecular structurecrystal structure -(opto)electronic properties" relationships, which are now in the focus of the material science.…”

Section: Introductionmentioning

confidence: 99%

Impact of N-substitution on structural, electronic, optical, and vibrational properties of a thiophene–phenylene co-oligomer

et al. 2020

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Unraveling the unusual effect of fluorination on crystal packing in an organic semiconductor

Abstract: Two-atom variation in the chemical structure of a naphthalene diimide derivative induced an unexpected crossover from pi-stacking to herringbone molecular packing.

Cited by 18 publications

References 64 publications

Non‐Local Electron‐Phonon Interaction in Naphthalene Diimide Derivatives, its Experimental Probe and Impact on Charge‐Carrier Mobility

Non‐Local Electron‐Phonon Interaction in Naphthalene Diimide Derivatives, its Experimental Probe and Impact on Charge‐Carrier Mobility

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

Impact of N-substitution on structural, electronic, optical, and vibrational properties of a thiophene–phenylene co-oligomer

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