Synergistic effects of halogen bond and π–π interactions in thiophene-based building blocks

Wilson, Jamey L.; Williams, Jon Steven Dal; Petkovsek, Chesney; Reves, Peyton L.; Jurss, Jonah W.; Hammer, Nathan I.; Tschumper, Gregory S.; Watkins, Davita L.

doi:10.1039/c5ra16680b

Cited by 13 publications

(17 citation statements)

References 39 publications

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“…Otheri ntermolecularf orces, such as p-type interactions, are known to compete with halogen bondingi nt he condensed phases [8,11] and are likely competing here with halogen bondingi nt hese solutions. Furthermore, as seen in Tables 1a nd 2, the j Dq j and rsvdW results of halogen-bonded complexesd isplay ac lear trend and track the increasing interaction strength.…”

Section: Discussionmentioning

confidence: 99%

“…Halogen-bondi nteractions with pyrimidine's nitrogen atoms shift normalm odes to higher energy and upfields hift 1 Ha nd 13 CNMR peaks in adjacent nuclei. [8,11] For example, we demonstrated that the crystal structures that result from using pyridyl thiophene-based donors exhibit strong halogen bond interactions, ranging from À7.5 to À8.7 kcal mol À1 , supplemented by other secondary interactions including pstacking interactions. The unexpected observation of vibrational red shifts and downfield 13 CNMR shifts in some complexes suggestst hat other intermolecular forces such as p interactions are competing with halogenb onding.…”

Section: Introductionmentioning

confidence: 97%

“…[1,7,23,[26][27][28][29] We have recently taken advantageofthese interactions for the creation of co-crystals for optoelectronic device applications. [8,11] For example, we demonstrated that the crystal structures that result from using pyridyl thiophene-based donors exhibit strong halogen bond interactions, ranging from À7.5 to À8.7 kcal mol À1 , supplemented by other secondary interactions including pstacking interactions. In fact, the p-stacking interactions were slightly larger in magnitude than the halogen bond interactions for co-crystals containing (iodoethynyl)difluorobenzene.…”

Section: Introductionmentioning

confidence: 97%

“…[1][2][3][4][5][6][7][8][9][10][11] Halogen bondingisdefined by IUPAC as anoncovalent interaction involving the net attraction between an electrophilic region of ah alogen atom of am olecular entity and the nucleophilic region of another. [1][2][3][4][5][6][7][8][9][10][11] Halogen bondingisdefined by IUPAC as anoncovalent interaction involving the net attraction between an electrophilic region of ah alogen atom of am olecular entity and the nucleophilic region of another.…”

Section: Introductionmentioning

confidence: 99%

“…The inclusion of halogen-bonded interactions in self-assembled materialb uildingb locks has recently garnered ag reat deal of attentionf or enhanced and selectivem orphological control. [1][2][3][4][5][6][7][8][9][10][11] Halogen bondingisdefined by IUPAC as anoncovalent interaction involving the net attraction between an electrophilic region of ah alogen atom of am olecular entity and the nucleophilic region of another. [12] Here, ah alogen bond acceptor is am olecule with an electron-rich region, such as the nitrogen atoms on pyrimidine, which interacts with ap ositive region of electrostatic potential (ESP) on ah alogena tom on an adjacent molecule.…”

Section: Introductionmentioning

confidence: 99%

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Quantifying the Effects of Halogen Bonding by Haloaromatic Donors on the Acceptor Pyrimidine

et al. 2017

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The effects of intermolecular interactions by a series of haloaromatic halogen bond donors on the normal modes and chemical shifts of the acceptor pyrimidine are investigated by Raman and NMR spectroscopies and electronic structure computations. Halogen-bond interactions with pyrimidine's nitrogen atoms shift normal modes to higher energy and upfield shift H and C NMR peaks in adjacent nuclei. This perturbation of vibrational normal modes is reminiscent of the effects of hydrogen bonded networks of water, methanol, or silver on pyrimidine. The unexpected observation of vibrational red shifts and downfield C NMR shifts in some complexes suggests that other intermolecular forces such as π interactions are competing with halogen bonding. Natural bond orbital analyses indicate a wide range of charge transfer is possible from pyrimidine to different haloaromatic donors and computed halogen bond binding energies can be larger than a typical hydrogen bond. These results emphasize the importance in strategic selection of substituents and electron withdrawing groups in developing supramolecular structures based on halogen bonding.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Quantifying the Effects of Halogen Bonding by Haloaromatic Donors on the Acceptor Pyrimidine

et al. 2017

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Hydrophobicity regulation by a facial bromine substitution in MIL‐47(V) for highly selective adsorptive desulfurization

Xie

Guo

et al. 2022

AIChE Journal

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Metal organic frameworks (MOFs) have shown promising adsorptive desulfurization (ADS) capacity yet remains great challenges to maintain excellent performance in presence of water. Guided by the density function theoretical (DFT) calculations, we select bromine modified linkers with different substitution degrees to construct MIL‐47‐xBr to regulate the porosity and hydrophobicity. The optimized MIL‐47‐Br exhibits the highest saturation dibenzothiophene (DBT) capacity of 179.2 mgS g−1 from the hydrous oil, surpassing the record of all ADS adsorbents. Meanwhile, the excellent selectivity, adsorption kinetics, and recycle stability endow MIL‐47‐Br with superior ADS performance from the commercial hydrous gasoline. With the DBT capacity decreases by only 12.3% from the commercial gasoline, a continue flow ADS is successfully achieved on the fixed‐bed of MIL‐47‐Br column. Therefore, this facial strategy of simple substitution can fully exploit the functions of open metal sites for enhancing the task‐specific selectivity, and has a promising application prospect in industrial ADS.

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Halogen Bonding in Halothiophene Building Blocks

Koivuporras,

Mailman,

Guo

et al. 2023

Crystal Growth & Design

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Thiophenes bearing monotopic and symmetric ditopic halogen substituents and asymmetric ditopic halogen and pyridine substituents that act as halogen bond acceptors were evaluated for their halogen bonding interactions with 1,4-diiodotetrafluorobenzene and N-iodosuccinimide. The combinations resulted in C/N–I···X′ (X′ = Cl, Br, I) and C/N–I···NPy (Py = pyridine) interactions, the former characterized by an interaction energy (ΔE int) ranging from −4.4 to −18.7 kJ mol–1 and the latter from −26.3 to −56.0 kJ mol–1. X-ray crystallography studies show that the ditopic asymmetric systems consisting of both halogens and pyridine self-associate through C–X···NPy (X = Cl, Br, I) halogen bonding, and in their optimized structures the energies range from −5.4 to −19.6 kJ mol–1 depending on the type of halogen atom present. The 1H NMR association constants of N–I···NPy halogen bonds range between 1405 and 6397 M–1. The σ-hole strengths of halogens have been useful in describing the interaction energies and solution models.

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Synergistic effects of halogen bond and π–π interactions in thiophene-based building blocks

Abstract: The use of a thiophene-based building block (Pyr-T) to achieve a supramolecular assembly driven by halogen bonding (XB) is described. X-ray crystallography, NMR, Raman spectroscopy, and computational chemistry afford evidence of strong XB and π–π stacking.

Cited by 13 publications

References 39 publications

Quantifying the Effects of Halogen Bonding by Haloaromatic Donors on the Acceptor Pyrimidine

Quantifying the Effects of Halogen Bonding by Haloaromatic Donors on the Acceptor Pyrimidine

Hydrophobicity regulation by a facial bromine substitution in MIL‐47(V) for highly selective adsorptive desulfurization

Halogen Bonding in Halothiophene Building Blocks

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