Multifacial Recognition in Binary and Ternary Cocrystals from 5-Halouracil and Aminoazine Derivatives

Portalone, Gustavo

doi:10.1021/acs.cgd.8b00662

Cited by 18 publications

(16 citation statements)

References 106 publications

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“…Hence, the larger electronegativity of X, the stronger hydrogen bond, while its angle X–H···Y tends to be linear. With marked directionality and strength, the hydrogen bond is the foundation of efficient supramolecular construction . It not only favors molecular packing structure prediction with a rational degree of accuracy, but also has been widely applied as a cement to build robust 1‐, 2‐, or 3D cocrystal networks.…”

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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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%

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

et al. 2019

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“…Adopting a cutoff value of 0.92 for the interaction ratio R XB [8], the ratio between the X• • • A (A = acceptor) contacts showing linear C-X• • • A disposition (bond angle > 155 • ) and the sum of vdW radii, 16 out of the 38 structures for 5Xuras and two out of the three structures for 6Xuras manifest weak linear XB interaction in which halogen atoms function as a XB donor. Out of the 18 structures showing XBs, 5-iodouracil and 6-chlorouracil can act as a XB donor only when cocrystallized with polar solvents [9,10] or with aminoazine derivatives [11]. Only eight structures containing the 5Xura fragment show XB interactions with nucleobases, with no clear evidence for the preferred nucleophilic oxygen, as in four structures O1 and in four structures O2 act as XB acceptors.…”

Section: Introductionmentioning

confidence: 98%

“…In a continuation of a long-term interest in crystal engineering of DNA/RNA bases [12][13][14][15][16][17][18][19][20][21] and in systems exhibiting halogen bonding via alternative donors [8,11], this work focuses on the XBs exhibited by pyrimidine nucleobases carrying at the C6 position a halogen atom and at the C2 and the C4 positions two nucleophilic oxygen atoms. This investigation was then extended to the two new polymorphs obtained for 5-chloro and 5-bromouracil and their (1:1) cocrystal (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Site Selectivity of Halogen Oxygen Bonding in 5- and 6-Haloderivatives of Uracil

Portalone

2019

Crystals

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Seven 5-and 6-halogenated derivatives of uracil or 1-methyluracil (halogen = Cl, Br, I) were studied by single crystal X-ray diffraction. In contrast with pure 5-halouracils, where the presence of N-H…O and C-H…O hydrogen bonds prevents the formation of other intermolecular interactions, the general ability of pyrimidine nucleobases to provide electron donating groups to halogen bonding was confirmed in three crystals and cocrystals containing uracil with the halogen atom at the C6 position. In the latter compounds, among the two nucleophilic oxygen atoms in the C=O moiety, only the urea carbonyl oxygen O1 can act as halogen bond acceptor, being not saturated by conventional hydrogen bonds. The halogen bonds in pure 6-halouracils are all rather weak, as supported by Hirshfeld surface analysis. The strongest interaction was found in the structure of 6-iodouracil, which displayed the largest (13%) reduction of the sum of van der Waals (vdW) radii for the contact atoms. Despite this, halogen bonding plays a role in determining the crystal packing of 6-halouracils, acting alongside conventional hydrogen bonds.

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“…Most reported OCTCs are binary compounds, consisting of an electron‐rich component and an electron‐deficient unit. The regular combination in a form of high‐crystallinity state (named as “co‐crystal”) resulted from the diverse intermolecular interactions and their competition, such as charge‐transfer forces, π–π interactions, [14] hydrogen bonds, [15] and sometimes halogen bonds [16] . Specially, heteroatoms in components could act as “arm‐lock” synthons to stable the 3D supramolecular interconnected network, [17] together with the adjustment of the degree of charge transfer (DCT) and the energy levels [18] …”

Section: Introductionmentioning

confidence: 99%

Multifunctional Features of Organic Charge‐Transfer Complexes: Advances and Perspectives

Wang

Luo

Peng

et al. 2020

Chemistry A European J

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The recent progress of charge‐transfer complexes (CTCs) for application in many fields, such as charge transport, light emission, nonlinear optics, photoelectric conversion, and external stimuli response, makes them promising candidates for practical utility in pharmaceuticals, electronics, photonics, luminescence, sensors, molecular electronics and so on. Multicomponent CTCs have been gradually designed and prepared as novel organic active semiconductors with ideal performance and stability compared to single components. In this review, we mainly focus on the recently reported development of various charge‐transfer complexes and their performance in field‐effect transistors, light‐emitting devices, lasers, sensors, and stimuli‐responsive behaviors.

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Multifacial Recognition in Binary and Ternary Cocrystals from 5-Halouracil and Aminoazine Derivatives

Cited by 18 publications

References 106 publications

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

Cocrystal Engineering: A Collaborative Strategy toward Functional Materials

Site Selectivity of Halogen Oxygen Bonding in 5- and 6-Haloderivatives of Uracil

Multifunctional Features of Organic Charge‐Transfer Complexes: Advances and Perspectives

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