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 Page 1 of 27 Physical Chemistry Chemical Physics
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Intermolecular interactions between σ- and π-holes of

Physical Chemistry Chemical Physics Accepted Manuscript

bromopentafluorobenzene and pyridine: computational and

experimental investigations

Fang-Ling Yang, Xing Yang, Rui-Zhi Wu, Chao-Xian Yan, Fan Yang, Weichun Ye, Liang-Wei Zhang,
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and Pan-Pan Zhou*

State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry

and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering,
*
Lanzhou University, 222 South Tianshui Road, 730000, Lanzhou, P. R. China. E-mail:

zhoupp@lzu.edu.cn

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Abstract

Physical Chemistry Chemical Physics Accepted Manuscript

The σ- and π-holes’ characters of bromopentafluorobenzene (C6F5Br) enable it to interact with

electron-rich atom or group like pyridine which possesses electron lone-pair N atom and π

ring. Theoretical studies of intermolecular interactions between C6F5Br and C5H5N have been
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carried out at the M06-2X/aug-cc-pVDZ level without and with counterpoise method,

together with single point calculations at the M06-2X/TZVP, wB97-XD/aug-cc-pVDZ and

CCSD(T)/aug-cc-pVDZ levels. The σ- and π-holes of C6F5Br exhibiting positive electrostatic

potentials make these sites favorably interact with the N atom and π ring of C5H5N with

negative electrostatic potentials, leading to five different dimers connected by σ-hole···n bond,

σ-hole···π bond or π-hole···π bond. Their geometrical structures, characteristics, nature and

spectroscopy behaviors were systematically investigated. EDA analyses reveal that the

driving forces in these dimers are different. NCI, QTAIM and NBO analyses confirm the

existence of intermolecular interactions formed via σ- and π-holes of C6F5Br and N atom and

π ring of C5H5N. The experimental IR and Raman spectra gave us important information

about the formation of molecular complexes between C6F5Br and C5H5N. We expect the

results could provide valuable insight into the investigations of intermolecular interactions

involving σ- and π-holes.

Keywords: σ-hole; π-hole; Electrostatic potential; Halogen bond; π···π interaction

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1. Introduction

It is well-established that covalently bonded halogen atom like Cl or Br atom

Physical Chemistry Chemical Physics Accepted Manuscript

possess unique amphoteric (nucleophilic as well as electrophilic) features,1, 2 so it can

serve as electron donor for forming hydrogen bond3-9 or as electron acceptor for
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forming halogen bond.10-20 In general, the halogen atom (e.g., Cl or Br atom) in a

molecule exhibits a region of positive molecular surface electrostatic potential (MSEP)

on the outermost portion of the halogen's surface, the so-called σ-hole,1, 2, 9, 21-33 which

enables it to interact with an atom (e.g., N or O atom) in a molecule with a region of

negative MSEP, generating halogen-bonding complex. Similarly, the aromatic π

system with strongly electron-withdrawing substituents can also have a positive MSEP

region, the so-called π-hole,22, 23, 26, 27, 33-40 which may act as an electron acceptor.

Bromopentafluorobenzene (C6F5Br) is an intriguing molecule possessing both the

σ- and π-holes because its Br atom can serve as halogen-bonding donor (i.e., σ-hole)41,

42
while its aromatic π ring can serve as an π-hole bonding donor (i.e., π-hole).20, 33, 37-39

Pyridine (C5H5N) is a six-membered heterocyclic compound containing one nitrogen

atom, so its N atom and the aromatic π system are good electron donors. In view of

these features, it can be expected that C6F5Br could interact with C5H5N via various

modes. Structurally, the Br atom of C6F5Br can interact with the N atom or the

aromatic π system of C5H5N by forming Br···N or Br···C halogen-bonding systems,

while the π-hole of C6F5Br can interact with the aromatic π system of C5H5N with π···π

interaction. Therefore, in this work, the possible interaction modes between C6F5Br

and C5H5N were taken into account, and their binding structures, spectroscopic and

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natures were systematically investigated. At the same time, the experimental IR and

Raman spectra were measured to understand the intermolecular interactions between

Physical Chemistry Chemical Physics Accepted Manuscript

C6F5Br and C5H5N. The results would provide valuable insights into the intermolecular

interactions involving the σ- and π-holes.

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2. Computational and Experimental Methods

2.1 Quantum mechanical calculations

The geometry structures of the monomers (C6F5Br, C5H5N) and complexes were optimized

using the M06-2X functional43, 44 with the aug-cc-pVDZ45 basis set. The counterpoise (CP)

method proposed by Boys and Bernardi46 was employed to take the basis set superposition

error (BSSE) correction into account. Harmonic vibrational frequency analysis was carried

out to ensure that the optimized structures were true minima without imaginary frequencies

on the potential energy surface. The interaction energy (∆Eint) is the energy difference between

the total energy of the complex and the sum of total energies of its constituent molecules. The

counterpoise interaction energy (∆Eint,CP) is the interaction energy (∆Eint) corrected by the

BSSE content of the interaction energy (δBSSE). Single point calculations at the

M06-2X/TZVP,47 wB97-XD48/aug-cc-pVDZ and CCSD(T)49/aug-cc-pVDZ levels of theory

were also performed. All the calculations in the work were implemented by using the

Gaussian 09 suite of programs.50

The molecular surface electrostatic potential (MSEP) was used to analyze the molecular

electronic property, which can be as a powerful tool to understand the formation of the

complex.31, 51-55 The energy decomposition analysis (EDA) method developed by Su and Li56

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was used to analyze the physically meaningful components of total interaction energy which

consists of electrostatic (Eelst), exchange (Eexch), repulsion (Erep), polarization (Epol) and

Physical Chemistry Chemical Physics Accepted Manuscript

dispersion (Edisp) (i.e., ∆Eint,EDA = Eelst + Eexch + Erep + Epol + Edisp.). The Eelst term is composed

of the attractive Coulomb interactions between the nuclei and electrons of the component
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monomers, the repulsive Coulomb interactions between the nuclei as well as between the

electrons of the component monomers, describing the Coulomb interactions among charge

densities of isolated monomers. The Eexch term originates from the electron exchange between

the component monomers due to the antisymmetric nature of a wave function. The Erep term

arises from other types of two-electron integral terms for molecular orbitals of the component

monomers. The overlap of monomeric wavefunctions leads to the depletion of electronic

density and increased nuclear repulsion, even though the exchange term is attractive the net

exchange-repulsion interaction is always repulsive. The Epol term is defined as the orbital

relaxation energy on going from the monomer Hartree-Fock spin orbitals to the

supermolecule Hartree-Fock spin orbitals, which reflects the effect of relaxation of the

monomeric wavefunctions. The Edisp term is derived from the correlation energy difference

between the supermolecule and the component monomers. The EDA calculations were carried

out at the M06-2X/aug-cc-pVDZ//M06-2X/aug-cc-pVDZ level of theory by employing the

GAMESS program.57 To understand the specific interaction types in the complexes, the

non-covalent interaction (NCI58, 59) analysis and quantum theory of atoms in molecules

(QTAIM60, 61) were employed. QTAIM can be used to analyze the bond critical points (BCPs)

forming in the intermolecular interactions like hydrogen bond, van der Waals, and π-π

interactions. The topology characteristics of the BCPs in the complexes were estimated using

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AIMAll (Version 09.11.29) program.62 The wave functions obtained at the

M06-2X/aug-cc-pVDZ level of theory have been analyzed using the Multiwfn software.63

Physical Chemistry Chemical Physics Accepted Manuscript

2.2 FT-IR spectra measurements

The FT-IR spectra were recorded on a FT-IR spectrophotometer (Nicolet Nexus 670, USA) by
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using liquid film method. The liquid films were prepared by dipping one drop of C6F5Br,

C5H5N, the mixed C6F5Br and C5H5N system (i.e., with volume ratios of 3:1, 1:1 and 1:3)

onto a blank KBr pellet. The compounds C6F5Br and C5H5N were purchased from

Adamas-beta, which is of analytic reagent grade.

2.3 Raman spectra measurements

The Raman spectra measurements were carried out at room temperature on Lab RAMHR800

with a Raman confocal microscopy system (Reni Shaw Microscope, laser excitation at 532

nm).

3. Results and Discussion

To understand how the intermolecular interaction occurs between C6F5Br and C5H5N, MSEP

analysis was employed to reveal their electronic properties. Then the possible interaction

modes were constructed and optimized to obtain the dimers, the vibrational frequencies and

interaction energies of the dimers were illustrated and discussed. EDA analysis was used to

unveil the driving forces for the formation of these dimers. NCI, QTAIM and NBO analyses

were used to characterize the dimers which provided detailed information about their nature.

Meantime, FT-IR, Raman and fluorescent spectra were measured to affirm the intermolecular

interactions formed between C6F5Br and C5H5N.

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As shown in Fig. 1, the MSEP contour surfaces for C6F5Br suggest that two positive

MSEP regions appear, one is on the outermost portion along the C−Br bond axis (i.e., σ-hole

Physical Chemistry Chemical Physics Accepted Manuscript

on the Br atom-end), the other is found on its aromatic π ring (i.e., π-hole), which are

consistent with the previous work.20, 37 For C5H5N, both the N atom and its aromatic π ring
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exhibit negative MSEP distributions. Their electronic features indicate that the σ-hole on Br

or π-hole on the π ring of C6F5Br with a positive MSEP region can interact with N atom or the

π ring of C5H5N with a negative MSEP region, so it can be expected that their interaction

modes via dimerization would possess many cases. Based on the MSEP analysis, we took all

possible interaction modes into account and constructed their structures for the geometry

optimization. Finally, our calculations suggest that the interactions between C6F5Br and

C5H5N can form five dimers, and their optimized geometries obtained at the

M06-2X/aug-cc-pVDZ level of theory are depicted in Fig. 2. Geometrically, dimer I is a

halogen-bonded complex via the Br···N interaction, dimers II and III are T-shaped or

edge-to-face structures but different from each other that there are "two legs" (i.e., one C–Br

bond and one C–F bond) standing above the C5H5N ring in dimer II while there is only "one

leg" (i.e., C–Br bond) of C6F5Br interacting with the C5H5N ring in dimer III. Note that the

C–Br bonds in dimers II and III pointing toward the N and C atoms of C5H5N, respectively.

The dimers IV and V are parallel-displaced or offset face-to-face π-π interactions but different

from each other that the C–Br bond of C6F5Br and the N atom of C5H5N in dimer IV (or V)

have the same or opposite direction in dimer IV or V, respectively.

Table 1 lists the geometrical parameters, stretching vibrational frequencies and

interaction energies for the five dimers obtained without and with the CP method. It can be

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seen that the geometrical parameters, stretching vibrational frequencies and interaction

energies are affected by the CP optimization. Compared to the optimized structures of dimers

Physical Chemistry Chemical Physics Accepted Manuscript

(I-V) obtained without the CP method, those obtained with CP method have minor difference

in the geometrical parameters and stretching vibrational frequencies of their C–Br bonds. But
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the distances of Br···N and Br···C interactions in dimers (I-III) are significantly influenced

by the CP method, which are longer than those obtained without the CP method. From Table 1,

it can be seen that the halogen-bonded dimer I via the Br···N interaction is stronger than the

T-shaped dimers II and III. The dimers IV and V are even stronger than dimers (I-III).

Evidently, the big π-hole on the π ring of C6F5Br with a positive MSEP region enables it to be

a better electron acceptor which interacts with N atom and the π ring of C5H5N with a

negative MSEP region by forming stronger π-π interactions in dimers IV and V. Thereby, the

interactions between C6F5Br and C5H5N would form more competitive π-hole intermolecular

interactions prior to σ-hole intermolecular interactions.

Compared to the interaction energies obtained at the M06-2X/TZVP and

wB97-XD/aug-cc-pVDZ levels, those obtained without the BSSE corrections for dimers (I-V)

are closer to those obtained at the wB97-XD/aug-cc-pVDZ level, those obtained with CP

method have larger deviations from those obtained at the wB97-XD/aug-cc-pVDZ level but

seem to be closer to those obtained at the M06-2X/TZVP level. Both the interaction energies

obtained without and with the BSSE corrections deviate from those obtained at the

CCSD(T)/aug-cc-pVDZ level. To further check the accuracy of the interaction energies

obtained without and with BSSE corrections, the energy decomposition analyses (EDA) based

on the geometries obtained at the M06-2X/aug-cc-pVDZ level without and with CP methods

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were also performed at the same level, and the total interaction energy (∆Eint, EDA) and five

terms (Eelst, Eexch, Erep, Epol and Edisp) were summarized in Table 2. It is clear that the ∆Eint, EDA

Physical Chemistry Chemical Physics Accepted Manuscript

values obtained based on the geometries without and with the CP optimizations are closer to

the interaction energies obtained without BSSE corrections. Therefore, the optimized
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geometries obtained without the CP method will be used for the following analyses.

From Table 2, EDA analysis can tell us the driving forces of the formation of dimers

(I-V). The terms of Eelst, Eexch, Epol and Edisp having negative values indicate that they are

attractive interactions which contribute to the stability of dimers (I-V). For dimer I, the

electrostatic (Eelst) interaction contributes significantly to its stability, which takes up about

32% of the total attractive component. The exchange (Eexch) and dispersion (Edisp) interactions

also make significant contributions (i.e., 27% and 26%, respectively), while the polarization

interaction has a contribution of 15%. Differently, with regard to dimers (II-V), the most

significant contribution is the dispersion (Edisp) interaction which accounts for 50-60%,

followed by Eexch, Eelst and Edisp. The four attractive interactions for dimers (I-V) countervail

the repulsive interaction (Erep), contributing to their stability.

To have an understanding of the intermolecular interactions in dimers I-V, NCI and

QTAIM analyses were employed. The reduced density gradient64 (s= 1/(2(3π2)1/3)|∇ρ|/ρ4/3) and

the electron density (ρ) multiplied by the sign of the second Hessian eigenvalue (λ2) of the

Laplacian ∇2ρ (i.e., sign(λ2)ρ) in NCI were used for the analyses. Generally, very small value

close to zero for the reduced density gradient is observed for the regions of noncovalent

interactions, low-gradient regions with smaller or larger densities are related to weak or

stronger (either stabilizing or destabilizing) interactions, respectively.65 The sign of λ2 can be

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utilized to distinguish the types of noncovalent interactions (i.e., bonded interaction (λ2< 0),

nonbonded interaction (λ2 > 0)). The quantity of sign(λ2)ρ with a small and negative value or

Physical Chemistry Chemical Physics Accepted Manuscript

a large and positive value is indicative of attractive or nonbonded interaction, while sign(λ2)ρ

with a value near zero indicates very weak, van der Waals interactions.59 The plots of s versus
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sign(λ2)ρ and the gradient isosurfaces for dimers (I-V) are depicted in Fig. 3. It can be seen

that the low-density and low-gradient spikes for dimer I are located at negative or positive

sign(λ2)ρ values in the vicinity of –0.015 or 0.020 a.u., which are indicative of strongly

attractive (i.e., Br···N halogen bond) or nonbonded (i.e., between central areas of C6F5Br and

C5H5N) interaction. The gradient isosurfaces for dimer I lies between the C–Br bond of

C6F5Br and N atom of C5H5N, characteristic of C–Br···N halogen-bonded interaction. For

dimers II and III, the low-density and low-gradient spikes locating at negative sign(λ2)ρ

values in the vicinity of –0.007 a.u. are indicative of strongly attractive interaction (i.e.,

Br···N halogen bond for dimer II and Br···C halogen bond for dimer III), while the

low-density and low-gradient spikes locating at positive sign(λ2)ρ values in the range of

0.020-0.025 a.u. are indicative of nonbonded interactions between central areas of C5H5N and

C6F5Br. In addition, the low-density and low-gradient spikes for dimers II and III locating at

positive sign(λ2)ρ values in the vicinity of 0.005 a.u. are indicative of weak and dispersive

attractions like van der Waals interactions. It is clear that the gradient isosurfaces which are

characteristic of C–Br···N (or C–Br···C) halogen-bonded interaction between the C–Br bond

of C6F5Br and N (or C) atom of C5H5N in dimer II (or III). The low-density and low-gradient

spikes for dimers IV and V locating at negative or positive sign(λ2)ρ values in the vicinity of

–0.005 or 0.005 a.u. are indicative of attractive π···π attractions, while the spikes locating at

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positive sign(λ2)ρ in the range of 0.020-0.025 a.u. suggest nonbonded interactions in the

central areas of C6F5Br and C5H5N. The green clouds of gradient isosurfaces between the π

Physical Chemistry Chemical Physics Accepted Manuscript

rings of C6F5Br and C5H5N are characteristic of their π···π interactions.

Moreover, the nature of intermolecular interactions in dimers (I-V) was explored based
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on the QTAIM analysis. The intermolecular BCPs are shown in Fig. 4, and their topological

parameters are listed in Table 3. It can be seen that dimer I possessing one intermolecular

Br···N BCP is C–Br···N halogen-bonded interaction. Dimer II possesses one Br···N and one

F···C intermolecular BCPs, corresponding to C–Br···N halogen-bonded interaction and F···C

van der Waals interaction, respectively. Dimer III is a C–Br···C halogen-bonded interaction.

Both dimers IV and V have four intermolecular BCPs, in which dimer IV has two BCPs

corresponding to π···π interactions, one BCP corresponding to F···C van der Waals

interaction and one BCP corresponding to C···N van der Waals interaction while dimer V has

BCPs corresponding to two π···π interactions, one BCP corresponding to C···N van der

Waals interaction and another BCP corresponding to Br···C van der Waals interaction.

Additionally, the sign of electronic energy density (H) was used to distinguish noncovalent

interactions, the positive (or negative) value is indicative of electrostatic (or covalent)

dominant interaction.66 All H values for dimers (I-V) are positive, suggesting the interactions

in these complexes are of primarily electrostatic character.

The above results suggest that dimers I and II are C–Br···N halogen-bonded interactions

while dimer III is C–Br···C halogen-bonded interaction, and dimers IV and V are π···π

interactions. To further uncover their interaction nature, natural bond orbital (NBO)67, 68

analysis was carried out to explore the intermolecular donor-acceptor orbital interaction in

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dimers (I-V). The orbital interaction between an electron donor orbital (i.e., "filled"

Lewis-type or bonding NBO) of one subsystem and an electron acceptor orbital (i.e., "empty"

Physical Chemistry Chemical Physics Accepted Manuscript

non-Lewis or antibonding NBO) of the other subsystem can give us more information about

their nature. For dimer I, the orbital interaction for C–Br···N halogen bond is σ-hole···n bond
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which occurs between lone pair orbital of N atom (i.e., LP(1)N) and σ antibonding orbital of

C–Br bond (i.e., BD*(1)C–Br) with a stabilization energy of 4.32 kcal/mol (Fig. 5a).

Although dimer II has a C–Br···N halogen bond, the orbital interactions suggest that a

stronger stabilization energy of 0.51 kcal/mol is observed for the electron delocalization from

the πC=N bonding orbital (i.e., BD(2)C–N) of C5H5N to the σC–Br antibonding orbital (i.e.,

BD*(1)C–Br) of C6F5Br (Fig. 5b), while the LP(1)N→BD*(1)C–Br orbital interaction has a

smaller stabilization energy of 0.06 kcal/mol (Fig. 5c), meaning that dimer II is actually

σ-hole···π bond. Dimer III connected by C–Br···C halogen-bonded interaction is σ-hole···π

bond, as can be seen from the orbital interactions between the two πC=C bonding orbitals of

C5H5N and the σC–Br antibonding orbital of C6F5Br (Fig. 5d and e). With respect to dimers IV

and V, they are π-hole···π bonds because the electron delocalizations occur between the πC=C

or πC=N bonding and antibonding orbitals of C6F5Br and C5H5N (Fig. 5f-k).

In general, the occurrence of intermolecular interaction between molecules is

accompanied by the changes of IR and Raman spectra of complex relative to that of

each molecule. Thereby, FT-IR and Raman spectra measurements for C6F5Br, C5H5N,

the mixed C6F5Br and C5H5N with volume ratios of 3:1, 1:1 and 1:3 were carried out.

as shown in Fig. 6. The three characteristic peaks at 1093, 1008, 983 cm-1 of FT-IR

spectrum for C6F5Br are in agreement with the previous report.69, 70 Compared to the

FT-IR spectra of C6F5Br and C5H5N, the peak changes for the mixed C6F5Br and

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C5H5N system appear in the range of 900-1100 cm-1, so such range of IR spectra are

shown here. We noted that the characteristic peaks of the mixed C6F5Br and C5H5N

Physical Chemistry Chemical Physics Accepted Manuscript

systems shifted slightly compared to those of C6F5Br and C5H5N, and the volume ratio

affected the peak shift. As one example, there is a peak at 1093 cm-1 (or 983 cm-1) of
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FT-IR spectrum for C6F5Br, but the peak has shifted to 1098 cm-1 (or 986 cm-1) of

FT-IR spectrum for the mixed C6F5Br and C5H5N system with volume ratio of 1:1.

Similar to the results from the FT-IR spectra, slight changes in Raman-shift of

experimental Raman spectra for the mixed C6F5Br and C5H5N systems were observed

in the range of 300-1300 cm-1 (Fig. 7). For instance, the peaks at 359 cm-1 for C6F5Br

and at 1030 cm-1 for C5H5N change to be 360 cm-1 and 1028 cm-1 for the mixed C6F5Br

and C5H5N system with volume ratio of 1:1. The previous reports suggest that the

formation of halogen-bonding interaction affects IR and Raman spectra.71, 72 Evidently,

in this work, the peak changes observed in FT-IR and Raman spectra for the mixed

C6F5Br and C5H5N systems indicate that these phenomena are closely associated with

the formation of intermolecular interaction between C6F5Br and C5H5N.

4. Conclusions

In summary, the intermolecular interactions between C6F5Br and C5H5N have been

explored based on the calculations at the M06-2X/aug-cc-pVDZ level of theory. The Br atom

and π ring of C6F5Br exhibit the intriguing σ- and π-holes’ characters, making them interact

with N or C atom or π ring of C5H5N by forming five different dimers. The dimers I and II

formed via σ-hole···n bonds are stronger than the one formed via σ-hole···π bond (dimer III),

while the dimers (IV and V) formed via π-hole···π bonds between the π-hole of C6F5Br and π

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ring of C5H5N are much stronger. The existences of these intermolecular interactions and their

nature have been confirmed and elaborated by NCI, QTAIM and NBO analyses. These dimers

Physical Chemistry Chemical Physics Accepted Manuscript

have different driving forces, as revealed by EDA analysis. The experimental FT-IR and

Raman spectra show that the slight peak changes are observed for the mixed C6F5Br and
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C5H5N systems which provide support to the formation of molecular complexes between

C6F5Br and C5H5N. We expect the results presented in this work are beneficial for the

investigations of intermolecular interactions involving σ- and π-holes.

Conflicts of interest

There are no conflicts to declare.

Acknowledgments

The work was financially supported by the National Natural Science Foundation of China

(Grant No. 21403097) and the Fundamental Research Funds for the Central Universities

(lzujbky-2014-182).

References

1. T. Clark, M. Hennemann, J. S. Murray and P. Politzer, J. Mol. Model., 2007, 13, 291-296.
2. P. Politzer, P. Lane, M. C. Concha, Y. Ma and J. S. Murray, J. Mol. Model., 2007, 13,
305-311.
3. N. Cheng, F. Bi, Y. Liu, C. Zhang and C. Liu, New J. Chem., 2014, 38, 1256-1263.
4. Q. Li, R. Li, Z. Zhou, W. Li and J. Cheng, J. Chem. Phys., 2012, 136, 014302.
5. Q. Li, Q. Lin, W. Li, J. Cheng, B. Gong and J. Sun, ChemPhysChem,2008, 9, 2265-2269.
6. S. A. C. McDowell, J. Chem. Phys., 2010, 132, 044312.
7. S. A. C. McDowell and D. S. Hamilton, Mol. Phys., 2015, 113, 1991-1997.
8. M. Solimannejad, M. Malekani and I. Alkorta, J. Phys. Chem. A 2010, 114, 12106-12111.
9. P. P. Zhou, W. Y. Qiu, S. Liu and N. Z. Jin, Phys. Chem. Chem. Phys., 2011, 13,
7408-7418.
10. G. Cavallo, P. Metrangolo, R. Milani, T. Pilati, A. Priimägi, G. Resnati and G. Terraneo,
Chem. Rev., 2016, 116, 2478-2601.
11. M. Fourmigue, Curr. Opin. Solid State Mater. Sci., 2009, 13, 36-45.

14
 Page 15 of 27 Physical Chemistry Chemical Physics
View Article Online
DOI: 10.1039/C8CP00420J

12. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati and G. Terraneo, Angew. Chem. Int. Ed.,
2008, 47, 6114-6127.
13. P. Metrangolo, H. Neukirch, T. Pilati and G. Resnati, Acc. Chem. Res., 2005, 38, 386-395.

Physical Chemistry Chemical Physics Accepted Manuscript

14. P. Metrangolo, W. Panzeri, F. Recupero and G. Resnati, J. Fluorine Chem., 2002, 114,
27-33.
15. X. Yang, C.-X. Yan, F. Yang, D.-G. Zhou, P.-P. Zhou and S. Liu, ChemistrySelect, 2017, 2,
2687-2699.
16. X. Yang, C.-X. Yan, D.-G. Zhou, F. Yang and P.-P. Zhou, RSC Adv., 2016, 6,
Published on 21 March 2018. Downloaded by Fudan University on 23/03/2018 11:48:36.

106285-106296.
17. X. Yang, F. Yang, R.-Z. Wu, C.-X. Yan, D.-G. Zhou, P.-P. Zhou and X. Yao, J. Mol.
Graph. Model., 2017, 76, 419-428.
18. X. Yang, P.-P. Zhou, F. Yang, D.-G. Zhou, C.-X. Yan, P.-J. Zheng and Y. Dai,
ChemistrySelect, 2016, 1, 1741-1750.
19. X. Yang, P.-P. Zhou, D.-G. Zhou, P.-J. Zheng, Y. Dai, C.-X. Yan and Z. Yang, Comput.
Theor. Chem., 2016, 1076, 32-41.
20. P.-P. Zhou, X. Yang, W. Ye, L.-W. Zhang, F. Yang, D.-G. Zhou and S. Liu, New J. Chem.,
2016, 40, 9139-9147.
21. T. Clark, Faraday Discuss., 2017, 203, 9-27
22. S. J. Grabowski, Phys. Chem. Chem. Phys., 2017, 19, 29742-29759.
23. L. Li, H. Wang, W. Wang and W. J. Jin, CrystEngComm, 2017, 19, 5058-5067.
24. S. A. C. McDowell, Chem. Phys., 2014, 598, 1-4.
25. J. S. Murray, P. Lane, T. Clark and P. Politzer, J. Mol. Model., 2007, 13, 1033-1038.
26. J. S. Murray, P. Lane, T. Clark, K. E. Riley and P. Politzer, J. Mol. Model., 2012, 18,
541-548.
27. V. d. P. N. Nziko and S. Scheiner, Phys. Chem. Chem. Phys., 2016, 18, 3581-3590.
28. P. Politzer, J. S. Murray and T. Clark, Phys. Chem. Chem. Phys., 2013, 15, 11178-11189.
29. P. Politzer, J. S. Murray and T. Clark, Top. Current Chem., 2015, 358, 19-42.
30. P. Politzer, J. S. Murray, T. Clark and G. Resnati, Phys. Chem. Chem. Phys., 2017, 19,
32166-32178.
31. P. Politzer, J. S. Murray and M. C. Concha, J. Mol. Model., 2007, 13, 643-650.
32. P. Politzer, J. S. Murray and M. C. Concha, J. Mol. Model., 2008, 14, 659-665.
33. H. Wang, W. Wang and W. J. Jin, Chem. Rev., 2016, 116, 5072-5104.
34. V. Angarov and S. Kozuch, New J. Chem., 2018, 42, 1413-1422.
35. A. Bauzá and A. Frontera, Phys. Chem. Chem. Phys., 2016, 18, 32155-32159.
36. L. Li, W. X. Wu, Z. F. Liu and W. J. Jin, New J. Chem., 2018, DOI:
10.1039/C1037NJ04536K.
37. X. Pang, H. Wang, W. Wang and W. J. Jin, Cryst. Growth Des., 2015, 15, 4938-4945.
38. X. Pang, H. Wang, X. R. Zhao and W. J. Jin, CrystEngComm, 2013, 15, 2722-2730.
39. X. Q. Yan, X. R. Zhao, H. Wang and W. J. Jin, J. Phys. Chem. B, 2014, 118, 1080-1087.
40. X. P. Zhang, X. C. Zhang, H. F. Dong, Z. J. Zhao, S. J. Zhang and Y. Huang, Energy
Environ. Sci., 2012, 5, 6668-6681.
41. V. V. Sivchik, A. I. Solomatina, Y.-T. Chen, A. J. Karttunen, S. P. Tunik, P.-T. Chou and I.
O. Koshevoy, Angew. Chem. Int. Ed., 2015, 54, 14057-14060.
42. S. Tsuzuki, A. Wakisaka, T. Ono and T. Sonoda, Chem. Eur. J., 2012, 18, 951-960.

15
 Physical Chemistry Chemical Physics Page 16 of 27
View Article Online
DOI: 10.1039/C8CP00420J

43. Y. Zhao and D. G. Truhlar, Acc. Chem. Res., 2008, 41, 157-167.
44. Y. Zhao and D. G. Truhlar, Theor. Chem. Acc., 2008, 120, 215-241.
45. T. H. Dunning Jr., J. Chem. Phys., 1989, 90, 1007-1023.

Physical Chemistry Chemical Physics Accepted Manuscript

46. S. F. Boys and F. Bernardi, Mol. Phys., 1970, 19, 553-566.
47. A. Schaefer, C. Huber and R. Ahlrichs, J. Chem. Phys., 1994, 100, 5829-5935.
48. J.-D. Chai and M. Head-Gordon, Phys. Chem. Chem. Phys., 2008, 10, 6615-6620.
49. J. A. Pople, M. Head-Gordon and K. Raghavachari, J. Chem. Phys., 1987, 87, 5968-5975.
50. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman,
Published on 21 March 2018. Downloaded by Fudan University on 23/03/2018 11:48:36.

G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li,

H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M.
Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao,
H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J.
Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K.
Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, N. J.
Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R.
Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W.
Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J.
Cioslowski and D. J. Fox, Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford CT,
2013.
51. V. Dimitrova, S. Ilieva and B. Galabov, J. Phys. Chem. A, 2002, 106, 11801-11805.
52. D. J. R. Duarte, M. M. de las Vallejos and N. M. Peruchena, J. Mol. Model., 2010, 16,
737-748.
53. E. Espinosa, C. Lecomte, N. E. Ghermani, J. Devemy, M. M. Rohmer, M. Bernard and E.
Molins, J. Am. Chem. Soc., 1996, 118, 2501-2502.
54. B. Galabov and P. Bobadova-Parvanova, J. Phys. Chem. A, 1999, 103, 6793-6799.
55. P. W. Kenny, J. Chem. Inf. Model., 2009, 49, 1234-1244.
56. P. Su and H. Li, J. Chem. Phys., 2009, 131, 014102-014115.
57. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S.
Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis and J. A.
Montgomery Jr., J. Comput. Chem., 1993, 14, 1347-1363.
58. J. Contreras-García, E. R. Johnson, S. Keinan, R. Chaudret, J.-P. Piquemal, D. N. Beratan
and W. Yang, J. Chem. Theory Comput., 2011, 7, 625-632.
59. E. R. Johnson, S. Keinan, P. Mori-Sánchez, J. Contreras-García, A. J. Cohen and W. Yang,
J. Am. Chem. Soc., 2010, 132, 6498-6506.
60. R. F. W. Bader, Atoms in Molecules: A Quantum Theory, Oxford University Press,
England, 1990.
61. R. F. W. Bader, Chem. Rev., 1991, 91, 893-928.
62. T. A. Keith, AIMALL Version 09.11.29, aim.tkgristmill.com, 2009.
63. T. Lu and F. Chen, J. Comput. Chem., 2012, 33, 580-592.
64. A. J. Cohen, P. Mori-Sánchez and W. Yang, Science, 2008, 321, 792-794.
65. G. V. Gibbs, D. F. Cox and K. M. Rosso, J. Phys. Chem. A, 2004, 108, 7643-7645.
66. W. D. Arnold and E. Oldfied, J. Am. Chem. Soc., 2000, 122, 12835-12841.
67. A. E. Reed, L. A. Curtiss and F. Weinhold, Chem. Rev. , 1988, 88, 899-926.

16
 Page 17 of 27 Physical Chemistry Chemical Physics
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68. A. E. Reed, R. B. Weinstock and F. Weinhold, J. Chem. Phys., 1985, 83, 735-746.
69. S. G. Frankiss and D. J. Harrison, Spectrochimi. Acta, 1975, 81, 1839-1864.
70. D. A. Long and D. Steele, Spectrochimi. Acta, 1963, 19, 1955-1961.

Physical Chemistry Chemical Physics Accepted Manuscript

71. G. R. Hanson, P. Jensen, J. McMurtrie, L. Rintoul and A. S. Micallef, Chem. Eur. J., 2009,
15, 4156-4164.
72. R. Liantonio, S. Luzzati, P. Metrangolo, T. Pilati and G. Resnati, Tetrahedron, 2002, 58,
4023-4029.
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Table 1 The geometrical parameters (R, d, in Å), stretching vibrational frequencies (v, in cm–1) and
interaction energies (∆Eint, in kcal mol–1) obtained without (non-CP) and with the CP methods for
C6F5Br and the dimers (I-V) at the M06-2X/aug-cc-pVDZ level of theory, and interaction energies

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(∆Eint-1, in kcal mol–1) at the M06-2X/TZVP//M06-2X/aug-cc-pVDZ level of theory, (∆Eint-2, in kcal
mol–1) at the wB97-XD/aug-cc-pVDZ//M06-2X/aug-cc-pVDZ level of theory, (∆ECCSD(T), in kcal mol-1)
at the CCSD(T)/aug-cc-pVDZ level of theory.
Method RC-Br vC-Br da ∆Eint b ∆Eint-1 c ∆Eint-2 d ∆ECCSD(T)e

I M06-2X/aug-cc-pVDZ non-CP 1.8773 245.0 2.9275 –4.88 –4.88 –4.96 –6.88

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CP 1.8780 244.4 2.9476 –4.18 (0.70) – – –

II M06-2X/aug-cc-pVDZ non-CP 1.8703 248.5 3.3655 –3.63 –2.70 –3.26 –5.38

CP 1.8708 248.3 3.3778 –2.92 (0.71) – – –

III M06-2X/aug-cc-pVDZ non-CP 1.8723 249.3 3.4072 –3.37 –2.28 –2.89 -4.87

CP 1.8728 248.9 3.7051 –2.68 (0.69) – – –

IV M06-2X/aug-cc-pVDZ non-CP 1.8690 249.1 3.3966 –7.72 –6.59 –7.58 –12.36

CP 1.8689 248.2 3.4415 –5.89 (1.83) – – –

V M06-2X/aug-cc-pVTZ non-CP 1.8716 246.0 3.4671 –8.04 –6.89 –8.35 –12.83

CP 1.8717 245.3 3.4645 –6.18 (1.86) – – –

C6F5Br M06-2X/aug-cc-pVDZ – 1.8709 245.0 – – – – –

a
For dimers I and II, the d is the Br···N distance, while for dimer III, the d is the Br···C distance. For
dimers IV and V, the d are the distances between the centers of the rings of C6F5Br and C5H5N (the d is
shown in Fig. 2).
b
The interaction energy obtained with CP method (∆Eint,CP) is the ∆Eint obtained without CP (non-CP)
method corrected by the BSSE energy (δBSSE), in which ∆Eint,CP=∆Eint+δBSSE. The value in the
parentheses is the δBSSE.
c
∆Eint-1 was obtained by the single point calculation at the M06-2X/TZVP level which is based on the
optimized geometry at the M06-2X/aug-cc-pVDZ level.
d
∆Eint-2 was obtained by the single point calculation at the wB97-XD/aug-cc-pVDZ level which is
based on the optimized geometry at the M06-2X/aug-cc-pVDZ level.
e
∆ECCSD(T) was obtained by the single point calculation at the CCSD(T)/aug-cc-pVDZ level which is
based on the optimized geometry at the M06-2X/aug-cc-pVDZ level.

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Table 2 EDA analysis of the physical components of total interaction energy (∆Eint,EDA, in
kcal mol-1) at the M06-2X/aug-cc-pVDZ//M06-2X/aug-cc-pVDZ(non-CP) and
M06-2X/aug-cc-pVDZ//M06-2X/aug-cc-pVDZ(CP) levels of theory for dimers I-V and the

Physical Chemistry Chemical Physics Accepted Manuscript

magnitudes of the attractive components.a
Complex Eelst (%) Eexch (%) Erep Epol (%) Edisp (%) ∆Eint,EDA
I non-CP -7.69 (32) -6.57 (27) 19.35 -3.68 (15) -6.43 (26) -5.02
CP -7.40 (32) -6.12 (27) 18.07 -3.53 (15) -6.02 (26) -5.00
II non-CP -2.61 (17) -3.12 (21) 11.51 -1.44 (9) -8.00 (53) -3.66
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CP -2.40 (17) -2.70 (19) 10.29 -1.36 (10) -7.46 (54) -3.62
III non-CP -2.29 (16) -2.96 (21) 10.79 -1.39 (10) -7.45 (53) -3.30
CP -2.06 (16) -2.54 (20) 9.66 -1.30 (10) -7.04 (54) -3.29
IV non-CP -5.35 (17) -6.30 (20) 23.83 -2.59 (8) -17.27 (55) -7.68
CP -4.68 (17) -5.14 (18) 20.52 -2.36 (8) -15.99 (57) -7.64
V non-CP -5.72 (18) -6.65 (21) 23.96 -2.92 (9) -16.80 (52) -8.13
CP -5.71 (18) -6.62 (21) 23.90 -2.92 (9) -16.78 (52) -8.13
a
The total attractive component is the sum of Eelst, Eexch, Epol and Edisp, while the magnitude in
parenthesis is the percentage of each component contributing to the total attractive
component.

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Table 3 The electron density (ρ) and Laplacian (∇2ρ), the Electronic Potential Energy Density (V),
the electronic kinetic energy density (G) and the electronic energy density (H) at the intermolecular
bond critical point (BCP) for dimers (I-V).a Units are in a.u..

Physical Chemistry Chemical Physics Accepted Manuscript

Complex BCP ρ ∇2ρ V G H

I BCP-1(Br···N) 0.01672 0.05478 -0.01054 0.01212 0.00158

II BCP-1(Br···N) 0.00773 0.02365 -0.00455 0.00523 0.00068

BCP-2(F···C) 0.00230 0.00919 -0.00118 0.00174 0.00056

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III BCP-1(Br···C) 0.00752 0.02240 -0.00379 0.00470 0.00091

IV BCP-1(C···C) 0.00668 0.01675 -0.00302 0.00360 0.00058

BCP-2(F···C) 0.00620 0.02371 -0.00387 0.00490 0.00103

BCP-3(C···C) 0.00632 0.01885 -0.00316 0.00394 0.00078

BCP-4(C···N) 0.00811 0.02434 -0.00450 0.00529 0.00079

V BCP-1(C···N) 0.00704 0.01997 -0.00388 0.00444 0.00056

BCP-2(C···C) 0.00746 0.02132 -0.00354 0.00444 0.00090

BCP-3(C···C) 0.00712 0.01991 -0.00332 0.00415 0.00083

BCP-4(Br···C) 0.00602 0.01560 -0.00277 0.00334 0.00057

a
The numbering for the intermolecular BCPs of dimers (I-V) is shown in Fig. 4.

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Fig. 1 The MSEP maps for C6F5Br and C5H5N mapped on the surface of molecular electron

density (isovalue=0.0004 a.u.) with MSEP values ranging from –0.025 to 0.025 a.u.

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Fig. 2 The optimized geometries for the dimers (a) I; (b) II; (c) III; (d) IV; (e) V at the

M06-2X/aug-cc-pVDZ level of theory without CP optimization.

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Fig. 3 Plots of the reduced density gradient (s) versus the electron density multiplied by the sign of
the second Hessian eigenvalue (sign(λ2)ρ) and the corresponding gradient isosurfaces (s=0.50 a.u.)
for dimers (I-V). The surfaces are colored on a blue-green-red scale in terms of the sign(λ2)ρ
values. The blue, green and red surfaces are indicative of strong attraction, weak and
nonbonded interactions, respectively.

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Fig. 4 The intermolecular BCPs for dimers (I-V).

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Fig. 5 The electron donor-acceptor orbital interactions for (a) dimer I; (b) dimer II; (c) dimer

II; (d) dimer III; (e) dimer III; (f) dimer IV; (g) dimer IV; (h) dimer V; (i) dimer V; (j) dimer

V; (k) dimer V.

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Fig. 6 FT-IR spectra for C6F5Br, C5H5N, the mixed C6F5Br and C5H5N with different

volume ratios.

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Fig. 7 Raman spectra for C6F5Br, C5H5N, the mixed C6F5Br and C5H5N with different

volume ratios.

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