Theoretical Investigations on Molecular Packing Motifs and Charge Transport Properties of a Family of Trialkylsilylethynyl-Modified Pentacenes/Anthradithiophenes

Zhang, Ning-Xi; Ren, Ai‐Min; Ji, Lingfei; Zhang, Shoufeng; Guo, Jian-You

doi:10.1021/acs.jpcc.8b06527

Cited by 18 publications

(17 citation statements)

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“…In order to understand the effect of −CF 3 and −CN on reorganization energy intuitively, the reorganization energies obtained by NM methods of three simple compounds, Ant , 1-A , and 2-A were first studied under gas-phase optimization. The NM analyses were executed by CT modeling package which is developed by our group. , The contributions of each vibration mode to hole/electron reorganization energies (λ h /λ e ) are shown in Table S3 and Figure S4. For Ant , the contributions for λ h mainly derive from the high-frequency region of C–H bending vibration (1421 cm –1 ) and CC stretching vibrations (1583 and 1683 cm –1 ).…”

Section: Resultsmentioning

confidence: 99%

Theoretical Investigations into the Electron and Ambipolar Transport Properties of Anthracene-Based Derivatives

Qin

Fan

et al. 2019

J. Phys. Chem. A

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To obtain anthracene-based derivatives with electron transport behavior, two series of anthracene-based derivatives modified by trifluoromethyl groups (−CF3) and cyano groups (−CN) at the 9,10-positions of the anthracene core were studied. Their electronic structures and crystal packings were also analyzed and compared. The charge-carrier mobilities were evaluated by quantum nuclear tunneling theory based on the incoherent charge-hopping model. Our results suggest that introducing −CN groups at 9,10-positions of the anthracene core is more favorable than introducing −CF3 to maintain great planar rigidity of the anthracene skeleton, decreasing more lowest unoccupied molecular orbital energy levels (0.45–0.55 eV), reducing reorganization energies, and especially forming a tight packing motif. Eventually, the excellent electron transport materials could be obtained. The molecule 1-B in Series 1 containing −CF3 groups is an ambipolar organic semiconductor (OSC) material with a 2D transport network, and its value of μh‑max/μe‑max is 1.75/0.47 cm2 V–1 s–1 along different directions; 2-A and 2-C in Series 2 with −CN groups are excellent n-type OSC candidates with the maximum intrinsic mobilities of 3.74 and 2.69 cm2 V–1 s–1 along the π–π stacking direction, respectively. Besides, the Hirshfeld surface and quantum theory of atoms in molecules analyses were applied to reveal the relationship between noncovalent interactions and crystal stacking.

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Section: Resultsmentioning

confidence: 99%

Theoretical Investigations into the Electron and Ambipolar Transport Properties of Anthracene-Based Derivatives

Qin

Fan

et al. 2019

J. Phys. Chem. A

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“…In organic semiconductors, the fast growth direction typically corresponds to the π-stack direction, with the π-plane representing a high-energy surface. Many small-molecule organic semiconductors, including trialkylsilylethynyl pentacenes, , N -trimethyltriindole, and copper phthalocyanine, form needle-like crystals in solution. In these crystals, the long axis of the needle corresponds to the π-stack direction, with the π-planes only exposed at the crystal tips.…”

Section: Optimizing the Orientation Of Organic Semiconductor Crystalsmentioning

confidence: 99%

Nanoconfining Optoelectronic Materials for Enhanced Performance and Stability

2019

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The solution processing of optoelectronic active layers promises to usher in a new era of technologies, from rollable displays to smart textiles, but critical challenges remain in the processing of these materials. While solutionbased deposition of these compounds, including organic small-molecules and polymers and metal−halide perovskites, is key to driving down manufacturing costs, the rapid, uncontrolled nature of solution processing invariably results in the formation of kinetically trapped films, with heterogeneities and defects spanning multiple length scales that degrade device performance. Given such finite time, usually on the order of seconds, for molecules to organize as solvent evaporates from the active layers, the use of nanoporous scaffolds to select for desired crystallization outcomes is a promising approach to addressing this critical issue. As the size of crystals decreases, their surface free energy plays an increasingly important role in dictating their morphology and structure. By confining crystallization within the sub-micrometer pores of scaffolds, such surface free energy effects can be exploited to select for specific polymorphs and crystal orientations. In this Perspective, we highlight the use of nanoporous scaffolds to stabilize high-performing polymorphs of metal-halide perovskites, as well as guide the orientation of organic semiconductor crystals both laterally and vertically for optimized in-plane and out-of-plane charge transport, respectively. Critically, examples of scalable solution-phase deposition methods using nanoporous scaffolds are highlighted as potential targets for commercialization.

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“…Since their seminal work, many others have utilized and expanded the packing motif concept to more PAHs and to aromatic molecules that have more chemical diversity than PAHs. This packing motif concept has been of particular relevance to the domains of organic electronics and energetics because of the observed correlations between these materials’ packing motifs and performance properties of interest (e.g., charge transport for organic semiconductors; insensitivity for molecular explosives). , However, despite the prevalence and utility of the packing motif concept, there is still no consensus as to how to quantitatively and accurately label them. Most often, such packing motif assignments are performed by individuals visually observing a crystal structure, rotating it, and making a best judgment as to which of the packing motif cartoons it most closely resembles.…”

Section: Introductionmentioning

confidence: 99%

Automated Identification of Molecular Crystals’ Packing Motifs

Loveland

Kailkhura

Karande

et al. 2020

J. Chem. Inf. Model.

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Packing motifspatterns in how molecules orient relative to one another in a crystal structureare an important concept in many subdisciplines of materials science because of correlations observed between specific packing motifs and properties of interest. That said, packing motif data sets have remained small and noisy due to intensive manual labeling processes and insufficient labeling schemes. The most prominent labeling algorithms calculate relative interplanar angles of nearest neighbor molecules to determine the packing motif of a molecular crystal, but this simple approach can fail when neighbors are naively sampled isotropically around the crystal structure. To remedy this issue, we propose an optimization algorithm, which rotates the molecular crystal structure to find representative molecules that inform the packing motif. We package this algorithm into an automated frameworkAutopackwhich both optimally rotates the crystal structure and labels the packing motif based on the appropriate neighboring molecules. In this work, we detail the Autopack framework and its performance, which shows improvements compared to previous state-of-the-art labeling methods, providing the first quantitative point of comparison for packing motif labeling algorithms. Furthermore, using Autopack (available at https://ipo.llnl.gov/ technologies/software/autopack), we perform the first large-scale study of potential relationships between chemicals' compositions and packing motifs, which shows that these relationships are more complex than previously hypothesized from studies that used only tens of polycyclic aromatic hydrocarbon molecules. Autopack's capabilities help pose next steps for crystal engineering research focusing not only on a molecule's adoption of a specific packing motif but also on new structure−property relationships.

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Theoretical Investigations on Molecular Packing Motifs and Charge Transport Properties of a Family of Trialkylsilylethynyl-Modified Pentacenes/Anthradithiophenes

Cited by 18 publications

References 85 publications

Theoretical Investigations into the Electron and Ambipolar Transport Properties of Anthracene-Based Derivatives

Theoretical Investigations into the Electron and Ambipolar Transport Properties of Anthracene-Based Derivatives

Nanoconfining Optoelectronic Materials for Enhanced Performance and Stability

Automated Identification of Molecular Crystals’ Packing Motifs

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