A new type of halogen bond involving multivalent astatine: an <i>ab initio</i> study

Zhou, Fengxiang; Liu, Yuan; Wang, Zhaoxu; Tian, Laijin; Yang, Qingyuan; Liu, Yi; Zheng, Baishu

doi:10.1039/c9cp02406a

Cited by 48 publications

(30 citation statements)

References 58 publications

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“…The (3,À 1) type of AIM CP is also known as bond critical point (BCP) and frequently employed to characterize chemical bonds and attractive weak interactions. [17][18][19][20][21] (3, + 1) and (3, + 3) types of AIM CPs correspond to ring critical point (RCP) and cage critical point (CCP), which are related to steric effect in small rings and cages, respectively. IRI has a close relationship with the AIM topology analysis, since both of them are able to provide insights into interatomic interactions in a chemical system.…”

Section: Relationship Between Iri Map and Aim Topology Analysismentioning

confidence: 99%

Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions**

Tian¹,

Chen²

2021

Chemistry Methods

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401

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Graphically revealing interaction regions in a chemical system enables chemists to quickly recognize where significant interactions have formed. Reduced density gradient (RDG) has already been widely employed in literatures to visually exhibit weak interaction regions, in fact it also has the ability of revealing chemical bonding regions. Unfortunately, RDG cannot clearly show both types of the interactions at the same time. In this work, we propose a new real space function named interaction region indicator (IRI), which is a slight modification on RDG. We found IRI can reveal chemical bonding and weak interaction regions equally well, which brings great convenience in the study of various chemical systems as well as chemical reactions. IRI is also compared with atom-in-molecules (AIM) topology analysis of electron density, it is demonstrated that IRI has the ability to reveal additional interactions to provide chemists a more complete picture. In addition, we put forward a variant of IRI named IRI-π, which is dedicated to reveal interactions of π electrons. It is found that IRI-π can not only distinguish type of π interactions but also exhibit πinteraction strength. IRI and IRI-π have been efficiently implemented in our freely available Multiwfn wavefunction analysis code (http://sobereva.com/multiwfn), and are expected to become new useful members of computational chemists' toolbox in studying chemical problems.

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Section: Relationship Between Iri Map and Aim Topology Analysismentioning

confidence: 99%

Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions**

Tian¹,

Chen²

2021

Chemistry Methods

Self Cite

763

401

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“…Among the halogen elements, astatine (At, Z = 85) is the heaviest naturallyo ccurringo ne, and it has been predicted to be the strongestX Bd onor atom, [8][9][10] despite the persistent lack of experimentald ata. However,w eh ave recently evidenced the first XBs involving At through the formation of adducts between astatine monoiodide( AtI) and several Lewis bases.…”

mentioning

confidence: 99%

Towards a Stronger Halogen Bond Involving Astatine: Unexpected Adduct with Bu₃PO Stabilized by Hydrogen Bonding

Liu

Guo

Champion

et al. 2020

Chemistry A European J

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The halogen bond is a powerful tool for the molecular design and pushing the limits of its strength is of major interest. Bearing the most potent halogen‐bond donor atom, astatine monoiodide (AtI) was recently successfully probed [Nat. Chem. 2018, 10, 428–434]. In this work, we continue the exploration of adducts between AtI and Lewis bases with the tributylphosphine oxide (Bu3PO) ligand, revealing the unexpected experimental occurrence of two distinct chemical species with 1:1 and 2:1 stoichiometries. The 1:1 Bu3PO⋅⋅⋅AtI complex is found to exhibit the strongest astatine‐mediated halogen bond so far (with a formation constant of 10(4.24±0.35)). Quantum chemical calculations unveil the intriguing nature of the 2:1 2Bu3PO⋅⋅⋅AtI adduct, involving a halogen bond between AtI and one Bu3PO molecular unit plus CH⋅⋅⋅O hydrogen bonds chelating the second Bu3PO unit.

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“…The charge transfer (CT) is another important factor that may determine HaB. The second-order perturbation energy (E(2)) and the charge transfer value (∆occ) can be used to measure the intermolecular interactions [ 51 ]. One can see that the formation of the C–X···O (X = Cl, Br, I) halogen bonds results from the orbital interaction between the halogen (X) or oxygen lone pair to the σ*(X–C) antibonding orbitals.…”

Section: Resultsmentioning

confidence: 99%

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

et al. 2021

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Structures of three tetrahalophthalic anhydrides (TXPA: halogen = Cl (TCPA), Br (TBPA), I (TIPA)) were studied by X-ray diffraction, and several types of halogen bonds (HaB) and lone pair···π-hole (lp···πh) contacts were revealed in their structures. HaBs involving the central oxygen atom of anhydride group (further X···O(anhydride) were recognized in the structures of TCPA and TBPA. In contrast, for the O(anhydride) atom of TIPA, only interactions with the π system (π-hole) of the anhydride ring (further lp(O)···πh) were observed. Computational studies by a number of theoretical methods (molecular electrostatic potentials, the quantum theory of atoms in molecules, the independent gradient model, natural bond orbital analyses, the electron density difference, and symmetry-adapted perturbation theory) demonstrated that the X···O(anhydride) contacts in TCPA and TBPA and lp(O)···πh in TIPA are caused by the packing effect. The supramolecular architecture of isostructural TCPA and TBPA was mainly affected by X···O(acyl) and X···X HaBs, and, for TIPA, the main contribution provided I···I HaBs.

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A new type of halogen bond involving multivalent astatine: an ab initio study

Abstract: Theoretical studies on the dimers formed by CO with the halides of multivalent astatine as a Lewis-acid center are carried out to examine the typical characteristics of supervalent halogen bonds.

Cited by 48 publications

References 58 publications

Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions**

Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions**

Towards a Stronger Halogen Bond Involving Astatine: Unexpected Adduct with Bu₃PO Stabilized by Hydrogen Bonding

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

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A new type of halogen bond involving multivalent astatine: an ab initio study

Abstract: Theoretical studies on the dimers formed by CO with the halides of multivalent astatine as a Lewis-acid center are carried out to examine the typical characteristics of supervalent halogen bonds.

Cited by 48 publications

References 58 publications

Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions**

Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions**

Towards a Stronger Halogen Bond Involving Astatine: Unexpected Adduct with Bu3PO Stabilized by Hydrogen Bonding

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

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Towards a Stronger Halogen Bond Involving Astatine: Unexpected Adduct with Bu₃PO Stabilized by Hydrogen Bonding