The Prominent Enhancing Effect of the Cation–π Interaction on the Halogen–Hydride Halogen Bond in M1⋅⋅⋅C6H5X⋅⋅⋅HM2

Li, Ran; Cheng, Jianbo; Liu, Zhenbo; Li, Wenzuo

doi:10.1002/cphc.201100237

Cited by 42 publications

(29 citation statements)

References 55 publications

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“…The applications of the Group V σ‐hole interactions in molecular recognition, crystal engineering, and biological systems are affected mainly by the strength and direction of the Group V σ‐hole interactions. The halogen bonds could display cooperative effect with other types of intermolecular interactions . Then, could the Group V σ‐hole interactions be strengthened by the addition of halogen bonds?…”

Section: Introductionmentioning

confidence: 99%

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH₃⋯NCX and OPH₃⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

Zeng

et al. 2015

J. Comput. Chem.

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The positive electrostatic potentials (ESP) outside the σ-hole along the extension of OP bond in OPH3 and the negative ESP outside the nitrogen atom along the extension of the CN bond in NCX could form the Group V σ-hole interaction OPH3 ⋯NCX. In this work, the complexes NCY⋯OPH3 ⋯NCX and OPH3 ⋯NCX⋯NCY (X, YF, Cl, Br) were designed to investigate the enhancing effects of Y⋯O and X⋯N halogen bonds on the P⋯N Group V σ-hole interaction. With the addition of Y⋯O halogen bond, the VS, max values outside the σ-hole region of OPH3 becomes increasingly positive resulting in a stronger and more polarizable P⋯N interaction. With the addition of X⋯N halogen bond, the VS, min values outside the nitrogen atom of NCX becomes increasingly negative, also resulting in a stronger and more polarizable P⋯N interaction. The Y⋯O halogen bonds affect the σ-hole region (decreased density region) outside the phosphorus atom more than the P⋯N internuclear region (increased density region outside the nitrogen atom), while it is contrary for the X⋯N halogen bonds.

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Section: Introductionmentioning

confidence: 99%

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH₃⋯NCX and OPH₃⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

Zeng

et al. 2015

J. Comput. Chem.

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“…[22] Theoretical calculations have also been widely used to investigate the nature and applications of XB. [1][2][3][4][23][24][25][26][27][28] Even though many levels of theory have estimated the strength of al ong list of XBs to be in the range of 0.04-1.20 eV, [29] they have hardly been investigated experimentally.T here is ad earth of experimental determinations of halogen bond strengths.G as-phase measurements of isolated systems has unique advantages to provide XB strengths that are in undisturbed local environments.I nt he current paper,w e present ag as-phase,m ass spectrometric and photoelectron spectroscopic study of the archetypical Br À -bromotrichloromethane complexes.I nC Cl 3 Br,t he Br atom exhibits as ignificant s-hole,m aking it ag ood XB donor.T he bromine anion is necessary to act as anegatively-charged non-covalent binding partner and to be able to apply the anion photoelectron spectroscopy.W em easured the photoelectron spectra of Br À (CCl 3 Br) 0-2 ,a nd utilized density functional theory (DFT) calculations to compare with our experimental values, to visualize the XBs,a nd to provide thermodynamic rationales to understand the formation of these complexes.Details of the experimental and theoretical methods are provided in the Supporting Information. Thep hotoelectron spectra of Br À and Br À (CCl 3 Br) taken with 266 nm (4.66 eV) laser and Br À (CCl 3 Br) 2 taken with 193 nm (6.42 eV) laser are presented in Figure 1.…”

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confidence: 99%

Spectroscopic Measurement of a Halogen Bond Energy

et al. 2019

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Halogen bonding (XB) has emerged as an important bonding motif in supramolecules and biological systems. Although regarded as astrong noncovalent interaction, benchmark measurements of the halogen bond energy are scarce. Here,acombined anion photoelectron spectroscopya nd density functional theory (DFT) study of XB in solvated Br À anions is reported. The XB strength between the positivelycharged s-hole on the Br atom of the bromotrichloromethane (CCl 3 Br) molecule and the Br À anion was found to be 0.63 eV (14.5 kcal mol À1 ). In the neutral complexes,B r(CCl 3 Br) 1,2 ,t he attraction between the free Br atom and the negatively charged equatorial belt on the Br atom of CCl 3 Br,w hich is as econd type of halogen bonding,w as estimated to have interaction strengths of 0.15 eV (3.5 kcal mol À1 )a nd 0.12 eV (2.8 kcal mol À1 ).Even though they are generally regarded as electron withdrawing groups,a lready covalently-bonded halogen atoms can in addition interact attractively and directionally by an on-covalent bond to neighbor nucleophiles such as lone pairs and anions. [1][2][3][4] This noncovalent interaction was first referred to as "halogen bonding" (XB) by Dumas and coworkers in 1976. [5,6] Halogen atoms have positive electrostatic potential regions on the opposite end of their s bond due to polarizability;m oreover,t he equatorial sides of these atoms exhibit negative electrostatic potential belts. [7,8] Thep ositive facial site was termed as "s-hole" by Politzer et al. in 2007, [9] although, clearly it is only apositive partial charge present at this site and no full electron is missing in any orbital. Thesize of the s-hole depends on the polarizability of the halogen atom, that is,I> Br > Cl > F, but it can also be tuned by other highly electron-withdrawing functional groups in the molecule. [2] While the positively-charged s-hole interacts with nucleophiles,the negatively-charged equatorial belt interacts with electrophiles,r esulting in two categories of XB inter-actions. [1] XB has rapidly expanded into applications such as crystal engineering. [10][11][12][13][14] It also has provoked the survey of biological structures,w here XB has been found to stabilize inter-a nd intramolecular interactions that can further affect ligand binding,p rotein folding,a nd enzymatic reactions. [15] While presence of XB interactions in the condensed-phase materials and biological chemistry is well known, experimental investigations of XB in the gas phase have been scarce. Nevertheless,t echniques such as molecular beam scattering, [16] rotational spectroscopy, [17][18][19] blackbody infrared radiative dissociation [20] and ion-mobility mass spectrometry have provided significant insight. [21] More recently,o ur group reported the stabilization of otherwise unstable anions by XB using gas-phase anion photoelectron spectroscopy. [22] Theoretical calculations have also been widely used to investigate the nature and applications of XB. [1][2][3][4][23][24][25][26][27][28] Even though many levels of theory have estimated th...

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“…[2,3] Cation···p interactions are conventionally considered as quadrupolar interactions between the aromatic ring and cations, though the charge-transfer component has been shown to be significant as well. [4][5][6][7][8] Based on such a simplistic picture, one might expect that both the top and bottom surfaces of the aromatic rings should bind to cations. Such an idea has been earlier used to describe aromatic rings that bind to cation and anion simultaneously.…”

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confidence: 99%

Do Cation⋅⋅⋅π Interactions Always Need to be 1:1?

2012

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The Prominent Enhancing Effect of the Cation–π Interaction on the Halogen–Hydride Halogen Bond in M¹⋅⋅⋅C₆H₅X⋅⋅⋅HM²

Cited by 42 publications

References 55 publications

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH₃⋯NCX and OPH₃⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH₃⋯NCX and OPH₃⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

Spectroscopic Measurement of a Halogen Bond Energy

Do Cation⋅⋅⋅π Interactions Always Need to be 1:1?

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The Prominent Enhancing Effect of the Cation–π Interaction on the Halogen–Hydride Halogen Bond in M1⋅⋅⋅C6H5X⋅⋅⋅HM2

Cited by 42 publications

References 55 publications

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH3⋯NCX and OPH3⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH3⋯NCX and OPH3⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

Spectroscopic Measurement of a Halogen Bond Energy

Do Cation⋅⋅⋅π Interactions Always Need to be 1:1?

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The Prominent Enhancing Effect of the Cation–π Interaction on the Halogen–Hydride Halogen Bond in M¹⋅⋅⋅C₆H₅X⋅⋅⋅HM²

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH₃⋯NCX and OPH₃⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH₃⋯NCX and OPH₃⋯NCX⋯NCY (X, YF, Cl, and Br) complexes