Practical crystal engineering using halogen bonding: A hierarchy based on calculated molecular electrostatic potential surfaces

Aakeröy, Christer B.; Wijethunga, Tharanga K.; Desper, John

doi:10.1016/j.molstruc.2014.02.022

Cited by 75 publications

(66 citation statements)

References 35 publications

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“…Nonetheless, Aakeroÿ and co-workers offered a solution to determine whether supramolecular synthons will either compete with or complement one another through the calculation of molecular electrostatic potentials of molecules. 182 Since electrostatics contribute greatly toward XB, much like HB, MEP calculations offer a good starting point for the researcher to determine which donors will prefer which acceptors on the basis of a simple electrostatic potentialbased ranking. This was experimentally confirmed by the cocrystallization of various XB donors with suitable acceptors, which cemented the assertion that XB follows the best donor− best acceptor rule analogously with HB.…”

Section: Predicting Xbsmentioning

confidence: 99%

Halogen Bonding in Supramolecular Chemistry

et al. 2015

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CONTENTS 1. Introduction to Halogen Bonding 7119 1.1. Nature of the Halogen Bond 7119 1.2. Scope of the Review 7120 2. Computational and Theoretical Investigations of Halogen Bonding 7120 2.1.Quantum Mechanics Methods 7120 2.2. σ-Hole Model of Halogen Bonding 7120 2.3. Other Contributions to the Nature of Halogen Bonding 7122 2.4. Recent Examples of Computationally Investigated Halogen-Bonded Complexes 7123 2.4.1. XB to Neutral Species 7123 2.4.2. XB to Anions 7126 2.4.3. XB in Protein−Ligand Complexes 7127 2.4.4. Electron-Transfer Processes Affected by XB Interactions 7127 2.5. Classical Force Field Calculations 7127 2.6. Conclusions and Outlook 7129 3. Gas-Phase Studies of Halogen-Bonding Interactions 7130 4. Halogen Bonding in the Solid State 7131 4.1. Introduction to Crystal Engineering and Functional Materials 7131 4.2. Fundamentals 7132 4.3. Halogen-Bonding Hierarchy 7134 4.3.1. Ranking Halogen-Bond Donors 7134 4.3.2. HB/XB Complementarity/Competition 7136 4.3.3. Predicting XBs 7138 4.4. Control of Solid-State Supramolecular Architectures 7138 4.4.1. Polymorphism 7138 4.4.2. Stoichiometry 7139 4.4.3. Tautomeric Control 7140 4.4.4. XBs Involving Metals and Metal-Bound XBs 7140 4.4.5. XB with Anions in the Solid State 4.5. Solid-State Architectures 4.6.

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Section: Predicting Xbsmentioning

confidence: 99%

Halogen Bonding in Supramolecular Chemistry

et al. 2015

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“…This 'activation" 12,13 includes adding one or more electron-withdrawing groups 14,15 to the molecular scaffold of the intended XB donor in order to promote depletion of negative charge from the σ-hole. 16 In this way, perfluorinated halogenbond donors, 17,18,19 nitro activated halogen-bond donors, 20 and cationic aromatic systems 21,22 have been employed successfully in XB-driven crystal engineering.…”

Section: Introductionmentioning

confidence: 99%

Crystal Engineering with Iodoethynylnitrobenzenes: A Group of Highly Effective Halogen-Bond Donors

Aakeröy

Wijethunga

Desper

et al. 2015

Crystal Growth & Design

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The benefits of employing a 'double activation' strategy for promoting effective practical cocrystal synthesis through halogen bonding was explored in a systematic supramolecular synthetic study of iodoethynylnitrobenzenes, where the positive electrostatic potential on the iodine atom was enhanced through a combination of an sp-hybridized carbon atom and one or more electronwithdrawing nitro groups. Three model compounds, 1-(iodoethynyl)-4-nitrobenzene (4N-I), 1-(iodoethynyl)-3-nitrobenzene (3N-I) and 1-(iodoethynyl)-3,5-dinitrobenzene (3,5DN-I) were synthesized and characterized, and calculated molecular electrostatic surface potential values on the halogen-bond donor site were about 20-40 kJ/mol higher than those observed for previously well-established halogen-bond donors. The ability of these molecules to drive co-crystal formation was evaluated through a total of 45 co-crystallization experiments with 15 different acceptor molecules. IR spectroscopic data for the resulting products showed that each reaction in the formation of a co-crystal driven by either C-I···N or C-I···O halogen bonds. The analogues bromo-compounds displayed a 60% success rate whereas the chloro-analogues did not yield any co-crystals, emphasizing the importance of the magnitude of the electrostatic aspects of halogen bonding for practical supramolecular synthesis. Ten new crystal structures are presented and the outcome (in terms of stoichiometry and connectivity) is largely predictable. A comparison of I···acceptor distances found in these structures with relevant data from the CSD shows that iodoethynylnitrobenzenes consistently give rise to a larger reduction of combined van der Waals radii (for C-X···acceptor) than do other well-known halogen bond donor moieties.

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“…To further rationalize the cocrystallization results, electrostatic surface potential (ESP) calculations were performed on the halogen‐bond acceptors. ESP has been proved to be an effective way of ranking the relative efficiency of halogen‐bonding interactions . Structures of all reported cocrystals of 1 / 2 with carbonyl compounds in the CSD were retrieved and ESP calculations were also performed on the halogen‐bond acceptors.…”

Section: Resultsmentioning

confidence: 99%

“…ESP has been proved to be an effective way of ranking the relative efficiency of halogen-bonding interactions. [24] Structures of all reported cocrystals of 1/2 with carbonyl compounds in the CSD were retrieved andE SP calculations werea lso performed on the halogen-bond acceptors.…”

Section: Esp Calculationsmentioning

confidence: 99%

Identification of an Overlooked Halogen‐Bond Synthon and Its Application in Designing Fluorescent Materials

Zhu

et al. 2019

Chemistry A European J

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Research on new supramolecular synthons facilitates the progress of materials design. Herein, the ability of sp2 carbonyl oxygen atoms to act as halogen‐bond acceptors was established through cocrystallization. Four sets of carbonyl compounds, including aldehydes, ketones, esters, and amides, were selected as halogen‐bond acceptors. In the absence of strong hydrogen bonds, 14 out of 16 combinations of halogen‐bond donors and acceptors could form cocrystals, whereby the supramolecular synthon C=O⋅⋅⋅X acts as the main interaction. Further, the geometric parameters of the C=O⋅⋅⋅X interaction were statistically revealed on the basis of the crystallographic database. The bifurcated interaction mode that has been observed in other halogen‐bond synthons rarely occurs in the case of C=O⋅⋅⋅X. The robustness of C=O⋅⋅⋅X makes its application in crystal engineering possible and opens up new opportunities in designing multicomponent fluorescent materials, as indicated by multicolor emission of cocrystals D through C=O⋅⋅⋅X interactions.

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Practical crystal engineering using halogen bonding: A hierarchy based on calculated molecular electrostatic potential surfaces

Cited by 75 publications

References 35 publications

Halogen Bonding in Supramolecular Chemistry

Halogen Bonding in Supramolecular Chemistry

Crystal Engineering with Iodoethynylnitrobenzenes: A Group of Highly Effective Halogen-Bond Donors

Identification of an Overlooked Halogen‐Bond Synthon and Its Application in Designing Fluorescent Materials

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