Twist‐Elasticity‐Controlled Crystal Emission in Highly Luminescent Polymorphs of Cyano‐Substituted Distyrylbenzene (βDCS)

Shi, Junqing; Yoon, Seong‐Jun; Viani, Lucas; Park, Soo Young; Milián‐Medina, Begoña; Gierschner, Johannes

doi:10.1002/adom.201700340

Cited by 35 publications

(44 citation statements)

References 38 publications

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“…As discussed above, the drastic changes in the crystal packing of the B‐ and G‐phase are accompanied by significant changes in the planarity of the molecules (Scheme ), being another example for the “twist elasticity” phenomena in DCS compounds as elaborated earlier . In both polymorphs, the molecules are substantially less twisted than expected for the free molecule (obtained by DFT; see Scheme ; for computational details, see the Supporting Information) to adapt to the external packing constraints, which are decided by the molecule's steric and electrostatic demands.…”

Section: Structure Of the B‐ And G‐thin Film Phasementioning

confidence: 83%

“…The latter gives −0.13 and −0.17 eV for the B‐ and G‐phase, respectively ( Table 1 ). At a quantum‐chemical basis, crystal shifts can be estimated from calculations of small clusters (nearest neighbor dimers or tetramers) versus the free monomers

Δ E_{cryst} = E (S_{1}, normalcluster) - E (S_{1}, normalmonomer)

…”

Section: Optical and Photophysical Propertiesmentioning

confidence: 99%

“…The device functionality of small‐molecule‐based organic optoelectronics depends strongly on the intermolecular arrangements as well as on morphological factors as intensively discussed in the past . This becomes apparent if the optical or electric response of different polymorphs of the same materials are considered . In particular, 2D arrangements—gathered via edge‐to‐face (herringbone) or slipped face‐to‐face (brickwork) packing motifs—were early realized as advantageous for efficient charge transport .…”

Section: Introductionmentioning

confidence: 99%

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Crossed 2D versus Slipped 1D π‐Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

Aliaga‐Gosalvez

Demitri

Dohr

et al. 2019

Advanced Optical Materials

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Polymorphs of organic semiconductors are of great interest as they shed light to structure-property relationships. The full X-ray thin film structure analysis of two polymorphs (B, G) of an important n-type semiconducting dicyanodistyrylbenzene based small molecule (CN-TFPA) is reported. Drastically different structures of the monotropic phases are revealed, that is an uncommon 2D crossed π-stacked arrangement for the B-phase versus a 1D slipped π-stack for G. Both phases exhibit a layered structure in the (100) plane with high structural integrity, driven by the hydrophobic contacts of the terminal CF 3 groups; as (100) coincides with the film surface, this allows for exfoliation by scotch tape. An in-depth time-dependent density functional theory (TD-DFT) based quantum mechanics/molecular mechanics (QM/MM) study reveals all subsequent significantly differing optical and electronic responses which result from the different arrangements: the B film shows little excitonic interaction with strong blue fluorescence, amplified spontaneous emission (ASE), and good 2D n-type transport. The G film forms H-aggregates with strong green fluorescence, no ASE, and 1D n-type charge transport. The established structure-property relationships are seen as a crucial step for computer-aided device analysis. Luminescent PolymorphsThe ORCID identification number(s) for the author(s) of this article can be found under https://doi.

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Section: Structure Of the B‐ And G‐thin Film Phasementioning

confidence: 83%

Δ E_{cryst} = E (S_{1}, normalcluster) - E (S_{1}, normalmonomer)

…”

Section: Optical and Photophysical Propertiesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Crossed 2D versus Slipped 1D π‐Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

Aliaga‐Gosalvez

Demitri

Dohr

et al. 2019

Advanced Optical Materials

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“…Crystal packing motifs in DSB single crystals were extensively explored by the introduction of a variety of substituents: methyl (Kabe et al, 2009;Varghese et al, 2013), tert-butyl (Gierschner et al, 2005), methoxy (Bartholomew et al, 2000), cyano (Bartholomew et al, 2000;Park et al, 2012), fluorine (Renak et al, 1999;Bartholomew et al, 2000;Gierschner et al, 2005), trifluoromethyl (Park et al, 2012;Varghese et al, 2016) and oher groups . Polymorph-dependent photoluminescence was previously realized by changing different intra-and intermolecular factors: N-HÁ Á ÁN interactions and hydrogen bonding (Zhang et al, 2006); conformational changes combined with -, C-HÁ Á ÁN, C-HÁ Á ÁF and C-HÁ Á Á interactions (Zhao et al, 2009;Wang et al, 2014;Chen et al, 2017); charge-assisted hydrogen bonding (Hinoue et al, 2012); O-HÁ Á ÁO hydrogen bonding (Hisamatsu et al, 2015); -, C-HÁ Á ÁO and C-HÁ Á Á interactions (Yuan et al, 2015); twisting,and C-HÁ Á Á interactions (Xu et al, 2016;Shi et al, 2017).…”

Section: Introductionmentioning

confidence: 99%

Crystal packing control of a trifluoromethyl-substituted furan/phenylene co-oligomer

Sonina

Koskin

Sherin

et al. 2018

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Furan/phenylene co-oligomer single crystals are considered as future materials for organic optoelectronics. Here, the effects of trifluoromethyl substituents on the crystallization, structure and optical properties of furan/phenylene cooligomer 1,4-bis{5-[4-(trifluoromethyl)phenyl]furan-2-yl}benzene are studied systematically. The solution growth methods and physical vapor transport result in the formation of three polymorphs depending on the growth method and the solvent. Single-crystal X-ray analysis reveals the crystal structures to correspond to H-, J-or mixed aggregates. All obtained crystals exhibit high photoluminescence efficiency and have optical properties which strongly depend on the crystal packing. Variable-temperature X-ray powder diffraction analysis shows the thermal transition of two forms (H-and J-aggregates) into a third one (mixed aggregate). Terminal trifluoromethyl groups induce weak intermolecular interactions which control the crystal packing and optical properties of co-oligomer single crystals.

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“…The Hex‐4‐TFPTA crystalline solid states (Figure a–c) showed a deep red (DR) emission of which the peak wavelengths were 683 and 631 nm (Figure d) for the single crystal and solid film, respectively. The extended π‐conjugation was longer than that of other DCS compounds, and the mesomeric effect (+M) of alkoxy substituents (Figure a) gave Hex‐4‐TFPTA the most redshifted emission.…”

Section: Extracted Photophysical/optical Parameters Of the Hex‐4‐tfptmentioning

confidence: 94%

Fabrication of Pixelated Organic Light‐Emitting Transistor (OLET) with a Pure Red‐Emitting Organic Semiconductor

Kim

Ryoo

et al. 2019

Advanced Optical Materials

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semiconductors with carrier mobilities insufficient to be useful for OLET applications. Therefore, developing high-purity red-emitting materials showing a high transistor mobility at the same time is a primary challenge to embodying highperformance OLETs in display devices.We have been exploring a broad library of dicyanodistyrylbenzene (DCS)-type materials that show excellent photoluminescence (PL) quantum efficiency and/or charge carrier mobility in the solid state by virtue of their unique stacking modes and propensity for strong self-assembly. [12,[18][19][20][21][22] Recently, we have specifically demonstrated that a charge-transfer (CT) cocrystal of DCS derivatives can be a light-emitting ambipolar semiconductor, which is ideally suitable for OLET applications. [23] Aiming at finding a potentially pure red-emitting organic semiconductor, we reviewed the whole DCS library, particularly for the π-extended ones. Fortunately, we came across Hex-4-TFPTA ((2E,2′E)-3,3′-(2,5-bis(hexyloxy)-1,4-phenylene) bis(2-(5-(4-(trifluoromethyl)phenyl) thiophen-2-yl)acrylonitrile) (Figure 1a), which has reportedly shown an excellent n-type mobility in a vacuum-evaporated film (µ e ≈ 2 cm 2 V −1 s −1 ) but with an unexplored photoluminescence property. [21] In this work, we decided to first investigate the photoluminescence properties of Hex-4-TFPTA and its application in the red-emitting OLET devices. We thoroughly investigated the photophysical properties of the crystal and solid thin film, in terms of intermolecular stacking mode (J-/H-aggregation), size of the crystal, and excimeric contributions. In addition, the electrical properties of Hex-4-TFPTA were properly reevaluated by introducing different metal electrodes to ensure a small contact resistance and to prevent the probable mobility overestimation [24,25] of organic field-effect transistors (OFETs) by their nonlinear transfer curve.Subsequently, Hex-4-TFPTA single-layered OLET devices were fabricated and characterized in terms of their charge transport and electroluminescence (EL). Finally, micropatterned pixels of the Hex-4-TFPTA OLET were fabricated by using a soft-lithographic technique called "patterned taping" [26] and employing a semitransparent electrode. [27,28] This report is actually the first example of pixelated emission from an OLET which was demonstrated by patterning the organic layer with a lithographic technique.The Hex-4-TFPTA crystalline solid states (Figure 1a-c) showed a deep red (DR) emission of which the peak wavelengths were 683 and 631 nm (Figure 1d) for the single crystal A pure red-emitting organic light-emitting transistor (OLET) is successfully fabricated using a π-extended dicyanodistyrylbenzene-type organic semiconductor material (Hex-4-TFPTA), which shows outstanding charge transport and solid-state luminescence at the same time. Based on the structural (X-ray) and photophysical analyses, it is found that the appropriate molecular stacking and highly allowed S 1 →S 0 transition of Hex-4-TFPTA created the ambidextrous balance between el...

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Twist‐Elasticity‐Controlled Crystal Emission in Highly Luminescent Polymorphs of Cyano‐Substituted Distyrylbenzene (βDCS)

Cited by 35 publications

References 38 publications

Crossed 2D versus Slipped 1D π‐Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

Crossed 2D versus Slipped 1D π‐Stacking in Polymorphs of Crystalline Organic Thin Films: Impact on the Electronic and Optical Response

Crystal packing control of a trifluoromethyl-substituted furan/phenylene co-oligomer

Fabrication of Pixelated Organic Light‐Emitting Transistor (OLET) with a Pure Red‐Emitting Organic Semiconductor

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