Experimental evidence of chalcogen bonding at oxygen

Fellowes, Thomas; Harris, Benjamin L.; White, Jonathan M.

doi:10.1039/c9cc09896h

Cited by 20 publications

(15 citation statements)

References 33 publications

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“…Der cantus firmus all dieser in dem vorliegenden Viewpoint beschriebenen Chemie sind nichtkovalente Wechselwirkungen von Lewis-aciden Chalkogen-Substituenten mit Lewis-Basen [31] -d ies kçnnen Chalkogene,H alogene oder auch Pnictogene sein. [32] Zusammengefasst wird dieses Phänomen heute unter dem prägnanten und eingängigen Begriff "Chalcogen Bonding". Der Begriff "Chalkogen-Chalkogen-Wechselwirkungen" war mitunter genauer, wollte man die nichtkovalente Wechselwirkung von Chalkogenen untereinander beschreiben, hat sich aber im Laufe der Zeit als zu sperrig erwiesen.…”

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Chemie und Begriffe entwickeln sich, aber Phänomene nicht: Von Chalkogen‐Chalkogen‐Wechselwirkungen zu “Chalcogen Bonding”

2020

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Chalcogen Bonding spielt in verschiedenen Bereichen der Chemie sowohl im Festkörper als auch in Lösung eine entscheidende Rolle. Bei genauer Literaturrecherche wird allerdings deutlich, dass – nachdem sich der Begriff von “Chalkogen‐Chalkogen‐Wechselwirkungen” zum prägnanteren “Chalcogen Bonding” verkürzt hatte – ein Teil der wissenschaftlichen Gemeinschaft sich an die Herkunft dieses Phänomens nicht mehr erinnert und dieses in seiner ursprünglichen Form auch nicht mehr referenziert. In diesem Viewpoint verfolgen wir exemplarisch die wissenschaftliche Entwicklung ausgehend von diesem Phänomen – beginnend mit seiner Entdeckung, über die Abänderung des Begriffs bis zur aktuellen und faszinierenden Forschung in Bereichen wie Crystal Engineering, dem Design supramolekularer Strukturen und der modernen Katalyse.

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Chemie und Begriffe entwickeln sich, aber Phänomene nicht: Von Chalkogen‐Chalkogen‐Wechselwirkungen zu “Chalcogen Bonding”

2020

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“…59 Some of the present authors have recently given experimental evidence of CB at oxygen in o-nitro-O-aryl oxime, which is a rare example of oxygen involvement. 72 Most systems induce CB through the aforementioned σ-hole but an analogous π-hole can also be the cause. A π-hole is a positive region of the electrostatic potential perpendicular to a planar π framework of the molecule.…”

Section: Introductionmentioning

confidence: 99%

The CHAL336 Benchmark Set: How Well Do Quantum-Chemical Methods Describe Chalcogen-Bonding Interactions?

Mehta¹,

Fellowes²,

White³

et al. 2021

Preprint

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<div> <div> <div> <p>We present the CHAL336 benchmark set—the most comprehensive database for the assessment of chalcogen-bonding (CB) interactions. After careful selection of suitable systems and identification of three high-level reference methods, the set comprises 336 dimers each consisting of up to 49 atoms and covers both σ- and π-hole interactions across four categories: chalcogen-chalcogen, chalcogen-π, chalcogen-halogen, and chalcogen-nitrogen interactions. In a subsequent study of DFT methods, we re- emphasize the need for using proper London-dispersion corrections when treating noncovalent interactions. We also point out that the deterioration of results and systematic overestimation of interaction energies for some dispersion-corrected DFT methods does not hint at problems with the chosen dispersion correction, but is a consequence of large density-driven errors. We conclude this work by performing the most detailed DFT benchmark study for CB interactions to date. We assess 98 variations of dispersion- corrected and -uncorrected DFT methods, and carry out a detailed analysis of 72 of them. Double-hybrid functionals are the most reliable approaches for CB interactions, and they should be used whenever computationally feasible. The best three double hybrids are SOS0-PBE0-2-D3(BJ), revDSD-PBEP86-D3(BJ), and B2NCPLYP-D3(BJ). The best hybrids in this study are ωB97M-V, PW6B95-D3(0), and PW6B95-D3(BJ). We do not recommend using any lower-rung DFT methods nor the popular B3LYP and MP2 approaches, which have been used to describe CB interactions in the past. We hope to inspire a change in computational protocols surrounding CB interactions that leads away from the commonly used, popular methods to the more robust and accurate ones recommended herein. We would also like to encourage method developers to use our set for the investigation and reduction of density-driven errors in new density functional approximations. </p> </div> </div> </div>

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“…The heavier chalcogen atoms (S, Se, and Te) form chalcogen bonds because the electron cloud of the chalcogen atom can be modified by an electron withdrawing substituent producing an electrophilic s-hole. [14] It is known that O forms chalcogen O…S and O•••O bonding interactions. [15] However, in the latter case only when highly activated oxygen acceptor atoms are involved.…”

Section: Introductionmentioning

confidence: 99%

“…As mentioned above, O is not considered to be a chalcogen bond acceptor. The heavier chalcogen atoms (S, Se, and Te) form chalcogen bonds because the electron cloud of the chalcogen atom can be modified by an electron withdrawing substituent producing an electrophilic s‐hole . It is known that O forms chalcogen O…S and O⋅⋅⋅O bonding interactions .…”

Section: Introductionmentioning

confidence: 99%

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Aromaticity and Chemical Bonding of Chalcogen‐Bonded Capsules Featuring Enhanced Magnetic Anisotropy

et al. 2020

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We present a theoretical study of chalcogen bonded container capsules (A X + A X) where X=O, S, Se, and Te, and their encapsulation complexes with n-C 9 H 20 (n-C 9 H 20 @A X + A X). Both Se and Te encapsulation complexes have significant experimental and computed binding energies, analogous to the hydrogen bonded counterparts, while the S and O capsules and their encapsulation complexes show only weak binding energies, which are attributed to different types of bonding: chalcogen S•••N bonds for S-capsules and π-π stacking and weak hydrogen bonds for the O case. All A X + A X and C 9 H 20 @A X + A X present unusually high magnetic anisotropies in their interiors. The 1 H NMR spectra of the encapsulation complexes display the proton signals of the encapsulated n-nonane highly upfield shifted, in agreement with the available experimental data for the Se capsule. We found that different factors contribute to the observed magnetic anisotropy of the capsule's interior: for the Te capsule the most important factor is Te's large polarizability; for the O analogue the inductive effects produced by the electronegative nature of the O and N heteroatoms; and for the S and Se capsules, the polarizability of the heteroatoms combines with electric field effects.

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Experimental evidence of chalcogen bonding at oxygen

Abstract: An o-nitro-O-aryl oxime was observed to exhibit a short O⋯O contact, which exhibited characteristics consistent with a chalcogen bond.

Cited by 20 publications

References 33 publications

Chemie und Begriffe entwickeln sich, aber Phänomene nicht: Von Chalkogen‐Chalkogen‐Wechselwirkungen zu “Chalcogen Bonding”

Chemie und Begriffe entwickeln sich, aber Phänomene nicht: Von Chalkogen‐Chalkogen‐Wechselwirkungen zu “Chalcogen Bonding”

The CHAL336 Benchmark Set: How Well Do Quantum-Chemical Methods Describe Chalcogen-Bonding Interactions?

Aromaticity and Chemical Bonding of Chalcogen‐Bonded Capsules Featuring Enhanced Magnetic Anisotropy

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