Amplified Halogen Bonding in a Small Space

Sarwar, Mohammed G.; Ajami, Dariush; Theodorakopoulos, Giannoula; Petsalakis, Ioannis D.; Rebek, Julius

doi:10.1021/ja407815t

Cited by 86 publications

(63 citation statements)

References 34 publications

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“…Selective coencapsulation of perfluoropropyl iodide and the XB acceptor pyridine or γ-picoline. 364 receptor and 2,6-dichloropyridine or 2,6-dibromopyridine in toluene ( Figure 101). 365 Since association constants were recorded in the region of 0.2−0.3 M −1 , the authors noted that large numbers of these XB interactions would be required to act in concert to form strong host−guest complexes.…”

Section: Inorganic Halogen-bond Donorsmentioning

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: Inorganic Halogen-bond Donorsmentioning

confidence: 99%

Halogen Bonding in Supramolecular Chemistry

et al. 2015

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“…Recently, in an elegant work by Fujita, Metrangolo, and Resnati, the authors highlighted that the confined space inside a self‐assembled cage enhances the halogen bonding between XB donors and XB acceptors. Previously, Rebek also showed that the encapsulation of both XB partners into the nanoconfined space of a dimeric capsule amplified the halogen‐bonding interaction and allowed its NMR characterization.…”

Section: Introductionmentioning

confidence: 99%

Synergic Interplay Between Halogen Bonding and Hydrogen Bonding in the Activation of a Neutral Substrate in a Nanoconfined Space

et al. 2019

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The principle of amplified halogen bonding (XB) in a small space is exploited as a catalytic tool for the activation of an XB acceptor substrate in a nanoconfined environment. The inner cavity of the resorcinarene capsule has been equipped with an XB catalyst bearing an ammonium unit acting as a Trojan horse to drive the catalyst inside the capsule. In the presence of a specific XB catalyst, the capsule is able to catalyze a Michael reaction between N‐methylpyrrole and methyl vinyl ketone. In the bulk medium in absence of the resorcinarene capsule, the XB catalyst is catalytically ineffective. Quantum‐mechanical investigations highlight that the Michael reaction proceeds through the activation of the carbonyl group by synergistically enhanced halogen/hydrogen‐bonding interactions and takes place in an open pentameric capsule.

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“…. Recent studies focus on theoretical as well as experimental investigations of hydrogen/halogen bonds in different confining environments …”

Section: Introductionmentioning

confidence: 99%

Quantum confinement in hydrogen bond

Santos

Filho

Ricotta

2015

Int J of Quantum Chemistry

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In this work, the quantum confinement effect is proposed as the cause of the displacement of the vibrational spectrum of molecular groups that involve hydrogen bonds. In this approach the hydrogen bond imposes a space barrier to hydrogen and constrains its oscillatory motion. We studied the vibrational transitions through the Morse potential, for the NH and OH molecular groups inside macromolecules in situation of confinement (when hydrogen bonding is formed) and non-confinement (when there is no hydrogen bonding). The energies were obtained through the variational method with the trial wave functions obtained from Supersymmetric Quantum Mechanics (SQM) formalism. The results indicate that it is possible to distinguish the emission peaks related to the existence of the hydrogen bonds. These analytical results were satisfactorily compared with experimental results obtained from infrared spectroscopy.

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Amplified Halogen Bonding in a Small Space

Cited by 86 publications

References 34 publications

Halogen Bonding in Supramolecular Chemistry

Halogen Bonding in Supramolecular Chemistry

Synergic Interplay Between Halogen Bonding and Hydrogen Bonding in the Activation of a Neutral Substrate in a Nanoconfined Space

Quantum confinement in hydrogen bond

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