Organic Three‐Component Single Crystals with Pseudo‐Isomorphic Cocrystallization for Nonlinear Optics and THz Photonics

Shin, Myeong‐Hoon; Lee, Seung‐Heon; Kang, Bong Joo; Jazbinšek, Mojca; Yoon, Woojin; Yun, Hoseop; Rotermund, Fabıan; Kwon, O‐Pil

doi:10.1002/adfm.201805257

Cited by 29 publications

(22 citation statements)

References 67 publications

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“…Recently, cocrystal materials have generally exhibited attractive performance with advanced applications in various fields . However, as a new design strategy toward functional materials, to realize targeted design toward functional cocrystal materials, it not only requires the coassembly processes to be understood, but also needs to explore the functionality‐related principles.…”

Section: Functionality‐related Fundamental Principles Of Organic Cocrmentioning

confidence: 99%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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materials, [9][10][11][12] which are crystalline singlephase materials composed of two or more different compounds generally in a stoichiometric ratio, [13] providing a platform for unveiling the structure-property relationships at a molecular level. [14] The building blocks are assembled via noncovalent interactions, offering the opportunity to achieve noncovalent synthesis of functional molecules. [15] Compared with the traditional covalent synthesis, cocrystal engineering offers numerous advantages, including: 1) avoiding complicated synthesis procedures, and cocrystal assemblies have been successfully fabricated by the vapor methods and solution-processing methods in a facile and low-cost way; 2) manipulating intermolecular interactions through selecting suitable conformers from a plentiful supply of raw materials, resulting in tunable structures, morphologies, and sizes; 3) achieving rare and multifunctional properties through a collaborative strategy in distinct constituent units, which are difficult to realize for individual components. [16][17][18] Cocrystal engineering began to draw much attention since the exploration of the metal conductive tetrathiafulvalene-7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) cocrystals in 1973. [19] The peculiar conductivity in organic materials makes it possible for cocrystals to serve as organic electrodes, which can effectively lower the contact resistance and further improve device performance. Encouraged by this, cocrystals can serve as a breakthrough and provide an opportunity to discover novel physicochemical properties, which are far beyond the performance of single materials. In this respect, dielectric response [20] and nonlinear optics [21,22] are also realized through rational design of each component, which is absent in their constitute components. Even more, the bottom-up supramolecular assembly provides the opportunity to equip them with the individual properties of the donor or acceptor to create multifunctional materials. [23] Typically, ambipolar charge transport can be generated by coassembling p-type semiconductors and n-type ones, and the charge-carrier mobility is now up to 1.57 cm 2 V −1 s −1 for holes and 0.47 cm 2 V −1 s −1 for electrons. [24] To date, these exciting results accelerate the investigations of organic functional cocrystals, such as room-temperature ferroelectricity, [25][26][27] optical waveguide properties, [28,29] pure organic room-temperature phosphorescent properties, [30][31][32] stimulusresponse (e.g., mechanical stress, [33,34] heat, [35,36] or solvent [37] ) characteristics, photovoltaics, [38] and near-infrared photothermal (PT) conversion and imaging, [39] etc.Cocrystal engineering with a noncovalent assembly feature by simple constituent units has inspired great interest and has emerged as an efficient and versatile route to construct functional materials, especially for the fabrication of novel and multifunctional materials, due to the collaborative strategy in the distinct constituent units. Meanwhile, the precise crystal a...

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Section: Functionality‐related Fundamental Principles Of Organic Cocrmentioning

confidence: 99%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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“…Cocrystals play an important role in the field of energetic materials (Aakerö y et al, 2015), nonlinear optics (Shin et al, 2018) and pharmaceuticals (Bolla & Nangia, 2016). The most widely useful applications of cocrystals are toward drug development, which may tune the physicochemical properties before transforming to an active ingredient at the site of biological action (Duggirala et al, 2016;Kavanagh et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

Multicomponent solid forms of the uric acid reabsorption inhibitor lesinurad and cocrystal polymorphs with urea: DFT simulation and solubility study

et al. 2019

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Lesinurad (systematic name: 2-{[5-bromo-4-(4-cyclopropylnaphthalen-1-yl)-4H-1,2,4-triazol-3-yl]sulfanyl}acetic acid, C 17 H 14 BrN 3 O 2 S) is a selective uric acid reabsorption inhibitor related to gout, which exhibits poor aqueous solubility. High-throughput solid-form screening was performed to screen for new solid forms with improved pharmaceutically relevant properties. During polymorph screening, we obtained two solvates with methanol (CH 3 OH) and ethanol (C 2 H 5 OH). Binary systems with caffeine (systematic name: 3,7-dihydro-1,3,7trimethyl-1H-purine-2,6-dione, C 8 H 10 N 4 O 2 ) and nicotinamide (C 6 H 6 N 2 O), polymorphs with urea (CH 4 N 2 O) and eutectics with similar drugs, like allopurinol and febuxostat, were prepared using the crystal engineering approach. All these novel solid forms were confirmed by XRD, DSC and FT-IR. The crystal structures were solved by single-crystal and powder X-ray diffraction. The crystal structures indicate that the lesinurad molecule is highly flexible and the triazole moiety, along with the rotatable thioacetic acid (side chain) and cyclopropane ring, is almost perpendicular to the planar naphthalene moiety. The carboxylic acid-triazole heterosynthon in the drug is interrupted by the presence of methanol and ethanol molecules in their crystal structures and forms intermolecular macrocyclic rings. The caffeine cocrystal maintains the consistency of the acid-triazole heterosynthons as in the drug and, in addition, they are bound by several auxiliary interactions. In the binary system of nicotinamide and urea, the acid-triazole heterosynthon is replaced by an acidamide synthon. Among the urea cocrystal polymorphs, Form I (P1, 1:1) consists of an acid-amide (urea) heterodimer, whereas in Form II (P2 1 /c, 2:2), both acidamide heterosynthons and urea-urea dimers co-exist. Density functional theory (DFT) calculations further support the experimentally observed synthon hierarchies in the cocrystals. Aqueous solubility experiments of lesinurad and its binary solids in pH 5 acetate buffer medium indicate the apparent solubility order lesinurad-urea Form I (43-fold) > lesinurad-caffeine (20-fold) > lesinurad-allopurinol (12-fold) ' lesinurad-nicotinamide (11-fold) > lesinurad, and this order is correlated with the crystal structures.

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“…In optical‐to‐THz conversion processes,8,9 benchmark organic nonlinear optical crystals simultaneously achieve high optical‐to‐THz conversion efficiency and broad bandwidth by using a diagonal optical nonlinearity from the nearly parallel alignment of nonlinear optical chromophores 10–16. For example, compared to widely used inorganic electro‐optic ZnTe crystals, organic ionic nonlinear optical crystals exhibit one order of magnitude higher THz generation efficiency, and over two times broader bandwidth, with an upper cut‐off frequency of >5 THz 17–20. This is possible in organic crystals due to their large diagonal component of macroscopic second‐order optical nonlinearity, and good phase matching between optical pump and generated THz waves 10…”

Section: Introductionmentioning

confidence: 99%

“…Most state‐of‐the‐art organic THz generators are based on optical configurations using a diagonal optical nonlinearity of benchmark organic crystals 10–20. The use of an off‐diagonal component of optical nonlinearity has rarely been investigated 21,22.…”

Section: Introductionmentioning

confidence: 99%

“…In many cases, off‐diagonal nonlinear optical components are negligibly small. Consequently, large diagonal optical nonlinearity with negligible off‐diagonal optical nonlinearity is commonly considered as optimal for electro‐optic and THz applications 12,15,19. For this reason, most previous studies for developing new organic THz generators are mainly targeted at achieving perfectly (or nearly) parallel alignment of nonlinear optical chromophores in solid state.…”

Section: Introductionmentioning

confidence: 99%

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X‐Shaped Alignment of Chromophores: Potential Alternative for Efficient Organic Terahertz Generators

Lee

Kim

Jazbinšek

et al. 2020

Advanced Optical Materials

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Efficient broadband organic terahertz (THz) generators using X‐shaped alignment of the nonlinear optical chromophores, as an alternative to the parallel alignment of chromophores in benchmark organic crystals, are reported. All the developed six organic benzothiazolium crystals exhibit an isomorphic X‐shaped alignment of chromophores, resulting in an unprecedentedly large off‐diagonal optical nonlinearity (>100 × 10−30 esu), which presents one of the largest off‐diagonal optical nonlinearity of organic crystals. The benzothiazolium crystals exhibit efficient broadband THz wave generation employing the off‐diagonal optical nonlinearity, in contrast to the present state‐of‐the‐art organic THz generators that mostly utilize diagonal optical nonlinearity. For using off‐diagonal and diagonal optical nonlinearities, the polarization of the optical pump is perpendicular and parallel, respectively, to the polar axis of crystals. In addition to a large THz wave generation efficiency with one order of magnitude higher peak‐to‐peak THz electric field than that generated in a 1.0‐mm‐thick inorganic benchmark ZnTe crystal, the benzothiazolium crystals generate broadband THz spectra with an upper cut‐off frequency of near 8 THz, and the absence of strong absorption dimples in the range of 0.5−4 THz. Therefore, the X‐shaped alignment of chromophores presents an interesting potential alternative for efficient broadband organic THz generators.

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Organic Three‐Component Single Crystals with Pseudo‐Isomorphic Cocrystallization for Nonlinear Optics and THz Photonics

Cited by 29 publications

References 67 publications

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

Multicomponent solid forms of the uric acid reabsorption inhibitor lesinurad and cocrystal polymorphs with urea: DFT simulation and solubility study

X‐Shaped Alignment of Chromophores: Potential Alternative for Efficient Organic Terahertz Generators

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