Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer

Narayanan, Ashwin; Cao, Dennis; Frazer, Laszlo; Tayi, Alok S.; Blackburn, Anthea K.; Sue, Andrew C.‐H.; Ketterson, J. B.; Stoddart, J. Fraser; Stupp, Samuel I.

doi:10.1021/jacs.7b02279

Cited by 77 publications

(51 citation statements)

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“…With the cooperation of the CT interaction and hydrogen bonds, the molecules are locked by a large‐scale network in a tightly packing mode, and that makes the cocrystal mechanically robust. More importantly, the cocrystals designed by this strategy could undergo room‐temperature ferroelectric polarization switching (Figure e) and realize two‐axes ferroelectric polarization (Figure f), which are unusual among organics.…”

Section: Rational Design and Controllable Preparation Of Organic Cocrmentioning

confidence: 99%

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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: Rational Design and Controllable Preparation Of Organic Cocrmentioning

confidence: 99%

Section: Rational Design and Controllable Preparation Of Organic Cocrmentioning

confidence: 99%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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“…Remarkably, the physical and chemical properties of co-crystals are not simply the sum of the molecular properties of their constituent molecular moieties [26,27]. In this regard, co-crystallization or crystallization of multi-component molecular systems (co-crystals, salts, and salt hydrates) opens the door not only for the development of new multifunctional materials but also for the examination of novel phenomenon such as charge-transfer along the molecular crystallographic axis [28,29].…”

Section: Of 22mentioning

confidence: 99%

Structure of Imidazolium-N-phthalolylglycinate Salt Hydrate: Combined Experimental and Quantum Chemical Calculations Studies

et al. 2020

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An organic supramolecular salt hydrate (imidazolium:N-phthalolylglycinate:H2O; IM+-NPG−-HYD) has been examined for its charge-transfer (CT) characteristics. Accordingly, IM+–NPG−–HYD has been characterized thoroughly using various spectroscopic techniques. Combined experimental and quantum chemical studies, along with wave function analysis, were performed to study the non-covalent interactions and their role in CT in the supramolecular salt hydrate. Notably, IM+–NPG−–HYD crystalizes in two configurations (A and B), both of which are held together via non-covalent interactions to result in a three-dimensional CT supramolecular assembly. The through-space CT occurs from NPG– (donor) to IM+ (acceptor), and this was mediated via non-covalent forces. We demonstrated the role of π–π stacking interactions (mixed-stacking donor-acceptor interactions) in the presence of charge-assisted hydrogen bonds in the regulation of CT properties in the self-assembly of the IM+–NPG−–HYD salt hydrate.

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“…On the contrary, practically all applicable inorganic ferroelectrics have several problems to overcome, such as toxicity, heavy weight, rare metal utilization, device fabrication cost, and others. The development of organic ferroelectrics is one of the potential approaches that might solve the above problems simultaneously, and a variety of organic materials have been developed in the areas of charge transfer, hydrogen bonding, simple cation‐anion exchange, and organic–inorganic hybrid crystals . A higher degree of design freedom for organic materials than that for the inorganic ones can allow facile expansion of the variety of materials and also mechanisms with which the order–disorder polarization inversion, such as proton transfer and supramolecular rotator, stores bits …”

Section: Figurementioning

confidence: 99%

“…The development of organic ferroelectrics is one of the potential approaches that might solve the above problems simultaneously,a nd av ariety of organic materials have been developed in the areas of charget ransfer,h ydrogen bonding, simple cation-anion exchange, and organic-inorganic hybrid crystals. [4][5][6][7][8][9][10] Ah igher degree of design freedom for organic materials than that for the inorganic ones can allow facile expansion of the varietyo fm aterials and also mechanisms with which the order-disorder polarizationi nversion,s uch as proton transfer and supramolecular rotator, stores bits. [11,12] Both the remanentp olarization (P r )a nd the coercive electric field (E c )a re important as the typicalf erroelectric parameters, which are associated with the ON/OFF ratio of as witching event,a nd an applied voltage in the memory device, respectively.F or instance, both the P r = 21 mCcm À2 and the E c = 29 kV cm À1 values of single-crystal croconic acid is superior to that of the P r = 15 mCcm À2 and E c = 85 kV cm À1 values for PZT.…”

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confidence: 99%