“Anti‐electrostatic” Halogen Bonding between Ions of Like Charge

Holthoff, Jana M.; Weiß, Robert; Rosokha, Sergiy V.; Huber, Stefan M.

doi:10.1002/chem.202102549

Cited by 30 publications

(34 citation statements)

References 153 publications

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“…After the formation of the carbocation intermediate, the possible X•••π complexes are enumerated as follows 46,47 : i) between two synthons; ii) one synthon as a XB donor and one carbocation intermediate as a XB acceptor; iii) one carbocation intermediate as a XB donor and one synthon as a XB acceptor; iv) between two carbocation intermediates. The concentration-dependent 1 H NMR spectrum shows that the interaction between two synthons is dominated by hydrogen bonds, thus excluding the complex i.…”

Section: Resultsmentioning

confidence: 99%

Multiselective gridization achieved by electrophilic C-X activation of dual halogen bonding cooperation

Xie

Wei

Zhong

et al. 2022

Preprint

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Organic science & technology (OST) become the frontier horizon after nanotechnology, information technology as well as biotechnology toward the era of consciousness. Organic nanogridarenes (ONGAs) are becoming robust nanoscaffolds for next-generation multifunctional/intelligent semiconductors with tunable cross-scale features. However, the prerequisite of trans-dimensional & intelligent design is to clarify the gridization rules for the discovery of the powerful molecular gridization protocols. Here, we report an efficient and multiselective Csp2-Csp3 gridization based on dual halogen bonding (X···π and X···S, X = Br, I) self-activated electrophilic substitution of halogenated electron-rich molecular blocks under supersonic conditions. Windmill-type nanogrids of cyclopenta[1,2-b:5,4-b']dithiophene (WG4) were obtained with the maximum path selectivity (96%), nanogrid-size selectivity (67%), site-selectivity (>99%) and moderate diastereoselectivity (WG4-1-6:WG4-2-6:WG4-3-6:WG4-4-6 =1:3.3:5.3:0), superior to the previous Friedel-Crafts gridization. Mechanistic studies have revealed the roles of XBs where the X···S bonding accelerates dehalogenation after electrophilic attack, and the X···π bonding leads to the multiselectivity of WG4. Impressively, C2-symmetric WG4-1-6 (21×21×15 Å) crystallizes into a Fd3̄c space group as the 16th pure organic molecules in CCDC library and hierarchically self-assemble into a complex 3D porous superstructure.

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Section: Resultsmentioning

confidence: 99%

Multiselective gridization achieved by electrophilic C-X activation of dual halogen bonding cooperation

Xie

Wei

Zhong

et al. 2022

Preprint

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“…In order to address the controversy in the literature 40,42,[46][47][48][49][50] as to whether a bond path between two H atoms signifies a stabilizing force, a pair of CH 4 molecules are aligned in a CHÁÁHC configuration. There has been a recent flurry of activity [51][52][53][54][55][56][57][58][59][60] dealing with the question as to whether a pair of ions of like charge can attract one another under certain circumstances, an issue which is addressed here by pairing the CN À and MgCl 3 À anions.…”

Section: Introductionmentioning

confidence: 99%

On the reliability of atoms in molecules, noncovalent index, and natural bond orbital to identify and quantify noncovalent bonds

Scheiner

2022

J Comput Chem

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Atoms in molecules, noncovalent index, and natural bond orbital methods are commonly invoked to identify the presence of various noncovalent bonds and to measure their strength. However, there are numerous instances in the literature where these methods provide contradictory or apparently erroneous interpretations of the bonding. The range of reliability of these methods is assessed by calculations of a variety of systems, which include an H‐bond, halogen bond, π‐tetrel bond, CH··HC interaction, and a pairing of two anions. While the results appear to be meaningful for the equilibrium geometries, and those where the two subunits are progressively pulled apart, these techniques erroneously predict a progressively stronger bonding interaction as the two units are compressed and the interaction becomes clearly repulsive. The methods falsely indicate a bonding interaction in the CH··HC arrangement, and incorrectly mimic the behavior of the energy when two anions approach. These approaches are also unreliable for understanding angular deformations.

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“…30–35 Again, the Coulombic repulsions between ions of like charge can be successfully countered by attractive short-range forces and lead to a stable complex. The bulk of these findings pertain to halogen bonds 36–46 but there are recent studies beginning to emerge that indicate similar sorts of attractive anion–anion interactions apply to pnicogen bonds 47 and to those between systems such as AuCl 4 − pairs. 48 Our own group has been actively engaged in studies to test the boundaries of these ideas.…”

Section: Introductionmentioning

confidence: 99%

Search for an exothermic halogen bond between anions

Scheiner

2022

Phys. Chem. Chem. Phys.

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“Anti‐electrostatic” Halogen Bonding between Ions of Like Charge

Abstract: Dedicated to Professor Frank Weinhold on occasion of his 80th birthday.

Cited by 30 publications

References 153 publications

Multiselective gridization achieved by electrophilic C-X activation of dual halogen bonding cooperation

Multiselective gridization achieved by electrophilic C-X activation of dual halogen bonding cooperation

On the reliability of atoms in molecules, noncovalent index, and natural bond orbital to identify and quantify noncovalent bonds

Search for an exothermic halogen bond between anions

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