Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

The study of hydrogen bonding and p  p interactions

in phenol  ethynylbenzene complex by IR spectroscopy
Danijela Vojta ⇑, Mario Vazdar
- Bošković Institute, Bijenička 54, 10001 Zagreb, Croatia
Division of Organic Chemistry and Biochemistry, Ruder

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 IR spectra of
phenol  ethynylbenzene hydrogen-
bonded complex were presented.
 Association constant of
phenol  ethynylbenzene complex is
determined.
 The direct involvement of C„C
moiety in hydrogen-bonded complex
is exhibited.
 The contribution of p  p interactions
in the complex is suggested.

a r t i c l e i n f o a b s t r a c t

Article history: Weak hydrogen bonds between phenol and ethynylbenzene in tetrachloroethene were explored by using
Received 10 February 2014 FTIR spectroscopy. Association constants (Kc) were determined by high dilution method at two temper-
Received in revised form 17 April 2014 atures, 20 °C and 26 °C, and they are, respectively, 0.54 ± 0.09 mol1 dm3 and 0.36 ± 0.08 mol1 dm3. The
Accepted 23 April 2014
position of ethynylbenzene stretching band, when in hydrogen bonding complex with phenol (C„C  ), is
Available online 5 May 2014
proposed to be governed by the interplay of OH  p (C„C moiety or phenyl ring of ethynylbenzene) and
p  p (phenyl ring of phenol  C„C moiety or phenyl ring of ethynylbenzene) interactions. This conclu-
Keywords:
sion is supported by the findings on the complex between ethanol and ethynylbenzene; in the latter,
Ethynylbenzene
Phenol
C„C   stretching band is shifted to the higher wavenumbers, as expected when ethynylbenzene inter-
Ethanol acts with hydrogen bond donor. Geometries and energies of the presumed complexes, as well as their
Hydrogen bonding vibrational spectra, are predicted by using ab initio calculations. The spectroscopic and thermodynamic
p  p interactions data obtained here offer the missing pieces in the present picture of migration of H-atom of phenol
IR spectroscopy OH group between competing hydrogen bond accepting centers on ethynylbenzene.
Ó 2014 Elsevier B.V. All rights reserved.

Introduction of the most inspiring systems where usual HB hierarchy pattern

In prediction of the structure and thermodynamical descriptors
of hydrogen bonded (HB) complexes a subtle balance between
weak HB centers on HB acceptor governs their interaction with
HB donors. In this context, ethynylbenzene (EB) emerged as one
⇑ Corresponding author. Tel.: +385 1 457 1220; fax: +385 1 168 0195.
E-mail address: dvojta@irb.hr (D. Vojta).
is not elusive. Although C„C group is considered to be more
attractive for H-atom than phenyl moiety, it is not always the pri-
mary site where HB is formed. UV–IR double resonance experi-
ments in the gas phase, combined with ab initio calculations at
MP2/aug-cc-pVDZ level of theory, shown that HB pattern formed
by EB, depending on the other protagonist of the HB complex,
was found to be diverse; cyclic structure of water  EB complex
was assumed to be the result of an interplay between OAH  p

http://dx.doi.org/10.1016/j.saa.2014.04.149
1386-1425/Ó 2014 Elsevier B.V. All rights reserved.
 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14
and O  HACH = HBs, where one water H-atom form HB with C„C
moiety of EB, while O-atom of water form HB with one of the ortho
atoms of phenyl ring [1]. In contrast, in simple alcohols like meth-
anol or ethanol, the complexation was presumed to be dictated by
the interaction of alcohol OH group with p system of phenyl ring,
and additional interaction of CH3 group with C„C moiety [2]. The
observed differences are rationalized in terms of domination of dis-
persion over electrostatics when H-atom is replaced with methyl
or ethyl group and the analogous phenomenon is observed in com-
plexes where EB interacts with ammonia and methylamine [3].
The ability of EB to form HB complexes with different partners
in solution was explored as well, although mostly expressed only
in terms of frequency shifts. In particular, West et al. studied the
position of „CAH   stretching band of EB as a function of differ-
ent HB acceptors like amides, while its HB donating character
was explored in interaction with phenol (PH) [4]. Furthermore,
the study of PH  EB interaction, conducted by Yoshida et al. [5],
was more detailed since they explored the temperature dependent
behavior of OH   stretching band of PH and estimated the thermo-
dynamical parameters of HB system from it.
HB patterns formed by PH and EB present intricate issue even
today, especially in the context of migration dynamics of PH
H-atom among two HB accepting sites (Fig. 1 with some possible
interaction patterns). When investigated chemical exchange of
D-atom of hydroxyl group of PH (OD group) by 2D IR spectroscopy,
Rosenfeld et al. [6] concluded that direct migration of D-atom
between HB accepting sites on a single EB molecule (C„C group
and phenyl ring) during 3–5 ps period is the only mechanism of
chemical exchange (Fig. 1a and b). Contrary to the direct migration
mechanism of PH along EB in CCl4 mixtures, ab initio calculations,
together with the simulations of molecular dynamics of PH sur-
rounded only with EB molecules [7], imply that indirect migration
mechanism is the main mechanism of chemical exchange and that
it dominates over direct migration. Indirect migration refers to the
intermolecular hopping of PH molecule from the HB accepting
site of one EB molecule (C„C group) to the another HB accepting
site on the another EB molecule (phenyl group); in such a three-
molecule complex, PH interacts with C„C moiety of one EB mole-
cule and phenyl ring of the another EB molecule. In turn, they
found that, when CCl4 is absent, dispersion is main interaction
force, while in the presence of CCl4, interaction between PH and
EB was found to be driven by both HB and dispersion forces,
p  p stacking in particular, and two-molecule complex (dimer)
is the most probable structure.
In contrast to the detailed investigation of the chemical
exchange kinetics, thermodynamics of HB between EB and PH is
rather incomplete. As far as the authors are aware, the only thermo-
dynamic values are those obtained by Yoshida et al. [5] and they
should be revisited due to several reasons. First, in experimental
conditions in which they worked, both of the compounds certainly
undergo self-association, as it has been pointed out in Refs. [8,9]. In
addition, PH  PH species, as well as higher polymers, produce the
broad features that span the part of the spectral range in which
EB  PH complex absorbs, making the measurements of the areas
below the bands disputable. Second, even if the self-association
Fig. 1. Possible interactions of phenol (PH) and ethynylbenzene (EB): (a) OH  p (C„C moiety) and p  p (phenyl ring  phenyl ring); (b) OH  p (phenyl ring); (c) OH  p
(phenyl ring) and p  p (C„C moiety   phenyl ring); and (d) OH  p (C„C moiety).
7
were avoided, the equilibrium concentration of every compound,
being determined from the correlation of the integrated absorption
intensities of the investigated bands and their positions [10], is con-
sidered not to be very accurate.
Thus, in order to get more accurate and detailed insight into
thermodynamics of PH  EB HB, high dilution method [11] will
be employed for determination of association constant, Kc. The lat-
ter will be measured at two temperatures, 20 °C and 26 °C, which
are considered to be lower and upper limit of usual room temper-
ature. Their difference will be briefly discussed and compared with
Kc values of other systems that have either PH as HB donor or EB as
HB acceptor in a HB complex.
Nonetheless, the direct involvement of C„C group in HB will be
exhibited and the mechanism that defines the position of C„C  
stretching band (associated C„C oscillator) will be proposed. The
importance of p  p interaction in PH  EB HB will be highlighted
by comparison of spectral shift of C„C   stretching band in the
EtOH  EB HB complex. The obtained experimental findings will
be supported with the ab initio calculations. The findings obtained
on the latter will shed more light on its recent research results as
well [2,3].
Experimental
Chemicals
Ethynylbenzene (EB, dark yellow liquid at room temperature,
b.p. = 142–144 °C, purity 99%) and tetrachloroethene (C2Cl4, col-
orless liquid at room temperature, b.p. = 122 °C, spectroscopic
grade), purchased from Alfa Aesar and, respectively, Acros
Organics, were used as received. Phenol (PH, white crystalline
solid at room temperature, m.p. = 40–41 °C, p.a. grade)
and ethanol (EtOH, colorless liquid at room temperature,
q(EtOH)20 °C = 0.7893 g cm3, b.p. = 78 °C, p.a. grade), purchased
from Kemika, were additionally purified by recrystallization
and, respectively, fractional distillation. Densities of EB and
C2Cl4 were determined by a densitometer DMA 5000-Anton
3
Paar: (q(EB)20 °C; 26 °C = 0.930187 g cm ; 0.924700 g cm3,
q(C2Cl4)20 °C; 26 °C = 1.622696 g cm ; 1.612728 g cm3).
3
Preparation of solutions
PH + EB in C2Cl4 mixtures
A set of 15 binary mixtures was prepared by dissolving EB in
C2Cl4. The concentrations of EB were: 0.090459 mol dm3 6
c0(EB) 6 1.17350 mol dm3. A set of 15 ternary mixtures was pre-
pared from corresponding binary mixture (EB in C2Cl4) and PH.
The concentration of PH in all ternary mixtures was in range
0.00312 mol dm3 6 c0(PH) 6 0.00996 mol dm1.
EtOH + EB in C2Cl4 mixtures
A set of 5 binary mixtures was prepared by dissolving EB in
C2Cl4 with concentrations of EB in range 0.19604 mol dm3 6
c0(EB) 6 0.90249 mol dm3. In a set of 5 ternary mixtures, after
8 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14
addition of EtOH (liquid) in every binary mixture, the EB’s
concentrations were in range 0.19600 mol dm3 6 c0(EB) 6
0.90233 mol dm3. The concentration of EtOH in all ternary mix-
tures was c0(EtOH) = 0.0069 mol dm3.
The first group of mixtures is prepared due to; (i) determination
of association constant (Kc) that characterize PH  EB HB by using
high dilution method and (ii) the analysis of certain spectral fea-
tures upon HB formation. The second group of mixtures is prepared
only for the reason (ii). More details on the high dilution method
and the performed spectral analysis are given in the Supplemen-
tary Materials.
FT IR spectra at room temperatures
IR spectra were measured on an ABB Bomem MB102 spectrom-
eter, equipped with CsI optics and a DTGS detector with nominal
resolution of 2 cm1 and 10 scans; the latter was found to be suf-
ficient for obtaining smooth enough IR spectra, especially OH
stretching band, for determination of the band absorbance, and,
at the same time, for preventing the accumulation of water from
the atmosphere which absorbs in the same spectral range and, con-
sequently, brings up the unreliability in the absorbance measure-
ments (Fig. S3 in Supplementary Materials). PH + EB in C2Cl4
mixtures were recorded at 20 °C and 26 °C (lower and achieved
upper limits of common room temperature interval), while EtO-
H + EB in C2Cl4 mixtures at 20 °C. The accuracy in temperature
measurement was ±1 °C.
IR measurements of solutions at room temperatures under
atmospheric pressure in air have been performed by using sealed
cells equipped with either KBr or CaF2 windows. In all the mea-
surements the cell’s path length was determined by Bertie’s proce-
dure using either dichloromethane (CH2Cl2) or benzene (C6H6) as a
secondary standard [12]. IR spectra of both binary and ternary mix-
tures concerned PH + EB in C2Cl4 mixtures were measured in cells
with d = 5090.25 lm (C6H6), d = 1003.35 lm and 102.25 lm (CH2-
Cl2). The data for each sample were collected three times in order
to calculate the uncertainty in the absorbance of PH’s OH stretch-
ing band and, consequently, the uncertainty in Kc. IR spectra of
both binary and ternary mixtures concerned EtOH + EB in C2Cl4
mixtures were recorded in CaF2 cell of d = 1001.19 lm (CH2Cl2)
and IR spectrum of each solution was recorded once. The repeated
measurements of the latter mixtures are considered to be unneces-
sary since only the positions of certain bands in their IR spectra are
to be determined and because the calculation of Kc for EtOH  EB
system is not the aim of this paper. Between measurements of dif-
ferent solutions, the cell was emptied, dried with N2, washed twice
with the studied solution; the cell is then refilled and the data were
recollected.
Calculations
Ab initio calculations were done at the MP2/aug-cc-pVDZ level
of theory for EtOH, PH, EB and corresponding complex structures.
Geometry optimizations and subsequent vibrational analysis for
all molecules was performed to verify that a minimum on the
potential energy surface was obtained. Complexation energies
(with included zero point vibrational energy) were calculated
using the supermolecular approach [13] as the difference between
complex and its constituents and corrected for basis set superposi-
tion error (BSSE) [14]. Due to harmonic approximation, i.e. the
neglect of anharmonicity in vibrational analysis, calculated vibra-
tional frequencies were scaled by the factor of 0.9604 in order to
better match experimental values [15]. All quantum chemical cal-
culations were performed employing Gaussian 03 [16].
Results and discussion
Calculations of PH, EtOH and EB as monomers, in HB complexes and
their vibrational frequencies
Quantum chemical MP2/aug-cc-pVDZ calculations predict that
three types of complex structures between EB and PH exist
(Fig. 2). The most stable complex, with complexation energy of
27.6 kJ mol1 is formed upon HB between PH hydroxyl group
with the C„CAH group of EB and simultaneous p  p stacking
interaction between benzene rings of EB and PH (structure 1). In
structure 2, only HB between OH group of PH and phenyl moiety
exists and there is no additional p  p stacking stabilization which
is evidenced by smaller stabilization energy of 18.2 kJ mol1. In
addition, OH group is not directed towards the center of phenyl
ring; instead it points to the bond between a pair of C-atoms so
it will be designated as OH  C@C. It is accompanied by the inter-
action of ortho H-atom of PH with a pair of C-atoms opposite to the
pair involved in the interaction with OH group. Finally, in structure
3 we observe two HB motifs, the first one between OH group of PH
with phenyl ring of EB and the second one where C„CAH group of
EB interacts with phenyl ring of PH. This structure is slightly more
stable than structure 2, but is however less stable than structure 1
with complexation energy of 19.9 kJ mol1.
Vibrational analysis of complexes 1–3 shows that there is a low-
frequency shift of 68–89 cm1 (depending on the complex) in
m~(OH) frequencies upon complexation of PH with EB compared to
neat PH solution (Table 1). This is in agreement with presented
experimental values where a similar low-frequency shift was
observed (Table 1). Overall, the comparison between experimental
and calculated frequencies is very good when the scaling factor of
0.9604 is used as suggested in [15].
IR spectra of binary mixtures
Alcohols in C2Cl4
The most relevant spectral feature used for determination of
association constant is OH stretching of unassociated PH in C2Cl4
observed at 3610 cm1. Possible self-association of PH can be
neglected since, as CCl4 concerns, which is considered to be very
similar to C2Cl4 [17,18], dimerization of PH starts at 0.1 mol dm3
[19]. However, according to Widom et al. [20], PH underwent
self-association already at c0(PH) = 0.003 mol dm3. As in the
majority of studies where PH act as HB donor the choice of
0.005 mol dm3 was considered as optimal [21], analytical concen-
trations used here in all solutions were between
0.003117 mol dm3 and 0.00996 mol dm3. Since at concentra-
tions smaller than c0(PH) = 0.001 mol dm3 OH stretching pro-
duces rather weak band with the absorbance unreliable to
quantify, it is not recommended to use smaller concentrations.
Molar absorption coefficient of OH stretching band at 3610 cm1
is e = 235 ± 1 mol1 dm3 cm1 [22]. OH stretching of unassociated
EtOH appears at 3635 cm1 [19], while dimers and polymers, cre-
ated at concentrations above, 0.01 mol dm3 and, respectively,
0.2 mol dm3, would absorb at, respectively, 3509 cm1 and
3336 cm1 in CCl4 at 25 °C [23]. Self-association is excluded at con-
centrations about 0.005 mol dm3 and, in this research, analytical
concentration of EtOH in all ternary mixtures was far below this
limit.
Ethynylbenzene (EB) in C2Cl4
Engagement of EB in HB is mostly expressed in the changes of
spectral features attributed to the vibrations of C„C moiety (when
in HB complex with HB donors like alcohols) or C„CAH moiety
(when in complex with HB acceptors). The former is observed as
 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14 9

Fig. 2. HB complexes between EB and PH (1–3) and EB and EtOH (1a and 2a). Complexation energies (corrected for BSSE) are given in parentheses.

Table 1
The positions and the tentative assignment of the vibrational modes of PH, EB, EtOH and HB complexes of PH and EB and, respectively, EtOH and EB in C2Cl4.

System m~a
OH OH   „CAH „CAH   C„C C„C  
Exp Calc Exp Calc Exp Calc Exp Calc Exp Calc Exp Calc
PH 3610 3656 – – – – – – – – – –
EB – – – – 3313 3343 – – 2113 2022 – –
EtOH 3634 3679 – – – – – – – – – –
PH + EB 3605 – 3572 3588d 3313 – – 3343d 2113 – 2113 2021c
3547 3579b 3340c 2015d
3533 3567c 3335b 2009b
3524
3513
EtOH + EB 3633 – 3656 3638e 3313 – – – 2113 – 2114–2115 2021e
3600 3638f 2016f
a
cm1.
b
Structure 1 (OH  C„C and p  p).
c
Structure 2 (OH  C@C and @CAH  p).
d
Structure 3 (OH  p and C„C  p).
e
Structure 1a (OH  phenyl).
f
Structure 2a (OH  C„C and ACH  p).

asymmetric band centered at 2113 cm1 in C2Cl4, while the latter
as complex envelope in the spectral range 3360–3260 cm1, with
maximum at 3313 cm1. The assignment and explanation of the
observed band shapes are offered in [24,25] and are out of the
scope of this paper. Self-association of EB, accomplished via HBs
between C„CAH and C„C groups at concentrations higher than
1.0 mol dm3, is evidenced by the appearance of new band at
about 3300 cm1 [9] assigned as C„CAH   stretching, while
C„C stretching band is generally less affected by the HB formation
[26]. Interaction between EB and PH studied in this paper was con-
ducted at analytical concentrations at which EB does not undergo
self-association, so that only PH  EB complex in stoichiometry
1:1 is expected. However, it should also be emphasized that EB
can participate in HB complex as HB acceptor employing either
through C„C bond or phenyl ring [27].
IR spectra of ternary mixtures
IR spectra of solutions that contain both PH and EB reveal some
features absent in IR spectra of solely PH or EB solutions; the OH
stretching band shifts for about 5 cm1 to the lower wavenumbers
when the concentration of EB is gradually increased and novel
broad feature arises at low frequency side of OH stretching with
EB’s concentration dependent intensities when compared with
solution containing only PH (Fig. 3a; black line designates PH in
C2Cl4 solution, while other lines correspond to the IR spectra of
PH + EB in C2Cl4 mixtures). The former effect may be attributed
to the solvent effects [18] because, when EB is present in the PH
solution at such high concentrations (in Fig. 3, in the range c0-
(EB) = 0.22552 mol dm3 (second lowest) 1.0766 mol dm3 (second
greatest)), the solvent is effectively being changed from pure C2Cl4
(3610 cm1) to the mixture of C2Cl4 and EB (3605 cm1). As the lat-
ter is concerned, although overall width and flatness of the feature
disables one to determine the number and position of the particu-
lar band with certain accuracy, from the second derivative spectra
(in the upper part of Fig. 3a with the spectral treatment more thor-
ough described in Supplementary Materials), it is estimated that,
aside the band at 3610 cm1, there are five more bands at the fol-
lowing positions: 3572 cm1, 3547 cm1, 3533 cm1, 3524 cm1
and 3513 cm1. According to the calculations, it is reasonable to
assume that the bands observed at 3572 cm1 (calc. 3588 cm1),
3547 cm1 (calc. 3579 cm1) and 3533 cm1 (calc. 3567 cm1)
10 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14

Fig. 3. IR spectra of PH + EB mixtures in C2Cl4 in the spectral ranges: (a) 3635–3505 cm1 (OH and OH   stretching) after C2Cl4 subtraction in 5090.25 lm cell (second
derivative spectra in the upper part of Fig. 3a); (b) 3360–3260 cm1 (C„CAH stretching) after C2Cl4 subtraction in 102.25 lm cell; and (c) 2170–2052 cm1 (C„C  
stretching) after EB + C2Cl4 subtraction in 1003.35 lm cell. In all figures the IR spectrum of PH solution without EB is shown as black line with the initial concentration of
c0(PH) = 0.00469 mol dm3. The initial concentration of PH in ternary mixtures presented in figures was in range 0.00312 mol dm3 6 c0(PH) 6 0.00996 mol dm1, while the
initial concentration of EB, respectively, was in range 0.22552 mol dm3 6 c0(EB) 6 1.0766 mol dm3. In Fig. 3b thicker line of the highest intensity designates the IR
spectrum of EB solution with the initial concentration of c0(EB) = 1.0766 mol dm3 which generates essentially the same spectrum as when PH is present and absent (thus, only
one solution is presented).

can be attributed to the stretching of OH oscillator involved in
three types of HBs, respectively: OH  p, OH  C„C and OH  C@C
(Table 1). The same assignment of the first two bands is also made
by Yoshida et al. [5] when studied association of PH and EB in CCl4.
Other two observed bands at 3524 cm1 and 3513 cm1 might be
attributed to the other PH  EB complexes, possibly with different
stoichiometry like 2:1. Although we have not dissolved PH in pure
EB [7], it is still plausible that certain amount of trimers exists.
The position and the shape of vibrational envelope attributed to
the C„CAH stretching band remains unchanged in the explored
concentration range (Fig. 3b). As, qualitatively, the envelope looks
the same as the one produced by EB in CCl4 solution when the
latter is present at much lower concentration (c0(EB) =
0.005 mol dm3, [9]), indicating that self-association of EB mole-
cules is avoided. In Fig. 3b, thicker band of the highest intensity
of EB in C2Cl4 solution completely overlaps with the spectrum of
PH + EB in C2Cl4 mixtures (c0(EB) = 1.0766 mol dm3), while black
line (PH in C2Cl4 solution) proves that PH does not absorb in this
spectral range. The subtraction of IR spectra of EB in C2Cl4 from
PH + EB in C2Cl4, when C„CAH stretching is to be captured in
the cell of d  100 lm, however, could not reveal any significant
residual. Thus, the eventual participation of C„CAH in HB com-
plex cannot be proved from these experiments. When discussing
the calculated vibrational spectra of three the most relevant
PH  EB complexes, it is interesting that only the third one (struc-
ture 3 in Fig. 2) does not predict the shift of the C„CAH stretching
band upon complexation (at calculated frequency of 3343 cm1
absorbs both unassociated and associated C„CAH oscillator).
Structures 1 and 2 exhibit low-frequency shift of the associated
C„CAH stretching oscillator, calculated to be at 3335 cm1 and,
respectively, at 3340 cm1 (Table 1).
Although the appearance of new band(s) attributed to the
stretching of an oscillator covalently bonded to H-atom and its
concentration dependence is usually considered to be necessary
and sufficient proof for the HB formation [28], it is interesting to
further deliberate the unambiguous evidence that C„C moiety
participates in HB formation.
After subtraction of binary from ternary mixture spectra
recorded in the same cell and at the same conditions
(1003.35 lm cell), in spectral range where C„C stretching absorbs
 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14
(2170–2052 cm1), a feature was observed which obviously origi-
nates due to the stretching of C„C oscillator directly involved in
HB with PH and assigned as C„C   (Fig. 3c), where    designates
association or participation in a HB complex. The position of this
band coincides with the position of unassociated C„C oscillator
within the limits of instrument uncertainty in wavenumber posi-
tion (2113 ± 1 cm1). As the change in the position of the band
involved in some kind of intermolecular arrangement usually sug-
gest the change in the band length upon complexation [29,30], the
absence of the shift, as well as the shift considered as negligible
when taking into account instrumental limitations, implies that
there is no change in the bond length of C„C moiety in spite of
the fact that HB is accomplished directly employing the latter.
The absence of the shift of C„C   stretching band when inter-
action is directly accomplished via C„C moiety might occur if
some other driving forces, aside presumed OH  p HBs
(OH  C„C), appear on the scene. The participation of p  p stack-
ing interactions between EB (phenyl ring) and PH (phenyl ring), as
explained by Rosenfeld et al. [6], may result with the observed
phenomenon. If this is the only event that takes place, then C„C
is effectively both HB donor and acceptor in the same molecule
because it transfers H-atom to the phenyl moiety and then takes
it back (Fig. 1a and b). This dual character may result with the can-
cellation of opposite effects of PH  EB HB on the C„C bond
stretching and lengthening and, in total, with unshifted C„C  
stretching band. However, the possibility of another scenario
should be considered as well and it is presented here for the first
time. It also accounts direct migration mechanism, although with
one important exception; the sliding of PH molecule along EB mol-
ecule is accompanied with the rotation of PH molecules around the
axis perpendicular to the plane formed by the complex PH  EB, so
there is a chance for participation of PH’s phenyl ring in association
as well (Fig. 1c and structure 3 in Fig. 2) In turn, delicate tuning
between HB and p  p interaction anticipates that both C„C and
phenyl groups are always involved in certain interaction, either
OH  p (p being C„C or phenyl ring) or p  p (phenyl ring of
PH  C„C or phenyl ring of EB). Detail band shape analysis of this
band is disabled due to two main reasons: (i) if this was the scope
of this paper the spectra should be collected with much greater
scan numbers. In this way, the noise would be reduced to the level
that it does not distort the signal in such an extent; (ii) C„C
stretching band profile, even when not involved in the HB complex,
is complicated feature by itself. Its natural asymmetry [24,25],
without the possibility of forming HB, was a long-lasting problem
for not only IR [31] but Raman spectroscopy as well [31,32]. Hence,
when involved in a HB complex, especially from the point of view
of low-resolution IR spectroscopy in solution, it becomes rather
tedious to discuss the asymmetry of the band attributed to the
stretching of C„C   oscillator. Thus, we will focus only on the
band position.
In contrast to the experimental observations, calculated vibra-
tional spectra of PH  EB HB complex, C„C moiety in particular,
reveal that C„C   stretching shifts to the lower frequencies upon
complexation; for the structure 2 (Fig. 2) the shift is the smallest
ðDm~ ¼ 1 cm1 Þ, while for structure 3 is Dm ~ ¼ 7 cm1 and,
respectively, the greatest shift is expected for structure 1
ðDm~ ¼ 13 cm1 Þ. According to the structure 2, C„C moiety of EB
is not involved in the HB complex with PH so, effectively, the struc-
ture 2 is not presumed to be responsible for the appearance of the
C„C   stretching band. The structures 3 and 1, due to the direct
engagement of C„C moiety in HB complex, may reproduce the
observed phenomenon. Moreover, the predictions of the stabiliza-
tion energies suggest that these two structures (structures 1 and 3
in Fig. 2) are the most stable ones. However, the absence of the
shift in experimental IR spectra still remains to be clarified. One
of the important factors is the influence of explicit solvent
11
molecules on HB formation (which is neglected here due to com-
putational expense) which certainly affects the interaction energy
between two compounds, especially when weak HBs with low
energies are investigated. Moreover, when the interplay of the var-
ious interactions (of which all are regarded as weak) is expected, it
follows that the bond length of an oscillator involved in HB does
not change. When taking into account mentioned disagreement
between predicted and experimentally observed spectra, as well
as of their possible explanations, due to smaller shift of C„C  
stretching in the structure 3 compared to structure 2 is predicted,
we attribute the observed phenomenon to the HB complex 3. The
likelihood that EB’s C„C group form p interaction with phenyl ring
is already reported on EB’s dimers, studied with both IR–UV double
resonance spectroscopy and ab initio calculations at different levels
of theory [33,34], where p-stacked antiparallel structure was found
to be the most stable.
If the influence of the HB and p  p stacking interplay on the
position of C„C   oscillator is to be unambiguously presented, it
is obligatory to conduct an analogous experiment on HB system,
similar to PH  EB, where p  p stacking interactions are elimi-
nated. As EtOH does not possess any other HB accepting center
besides OH group, only OH  p (where p designated either C„C
or phenyl group) are expected to be observed. Thus, mixtures of
EB with EtOH are further analyzed.
When EB is added to the solution of EtOH in C2Cl4 and its con-
centration is gradually increased, the band attributed to the EtOH
monomer (3634 cm1) becomes broader on the low-frequency side
and exhibits small shift of about 1 cm1 to the lower wavenum-
bers. Upon gradual increase of EB’s concentration, the asymmetry
of the OH stretching band appears suggesting the association of
EtOH and EB via OH group. The position of the OH   band is
assumed to be at 3600 cm1 (Fig. 4a). Aside the mentioned fea-
ture, a weak band at high-frequency side of monomer appears at
3656 cm1 (Table 1). Calculations found that two HB complexes
with different arrangement of EtOH and EB are the most stable
ones; the one in which the interaction is accomplished through
OH  phenyl interaction, as already suggested in [2] (structure 1a
in Fig. 2) and, respectively, through OH  C„C interaction (struc-
ture 2a in Fig. 2). However, the calculations predicted as well that
OH   stretching in both of the complexes produce the bands at
3638 cm1, i.e. shifted to the lower frequencies ðDm ~ ¼ 41 cm1 Þ
when compared with the band of the monomer EtOH
(3679 cm1). As IR–UV double resonance measurements suggested
that EtOH  EB HB complex is mainly established via OH  p (phe-
nyl) interaction (structure 1a in Fig. 2 in this paper), with low-fre-
quency shift of OH   stretching oscillator band [2], we will assign
the band at 3600 cm1 to the complex of the same geometry (1a
in Fig. 2). The band at 3656 cm1 will be, therefore, attributed to
the OH  C„C interaction (2a in Fig. 2) which is only briefly dis-
cussed in [2]. The high-frequency shift of the OH   stretching
oscillator band may be presumably due to the redistribution of
electron density, originating from C„C moiety, in EtOH molecule,
in a manner that only small amount of charge is kept in r⁄ orbital
of OH bond and that a larger amount is transferred on the ethyl
group [35,36]. As, according to the structure 2a, the H-atoms of
ethyl group may exert some kind of interaction with phenyl ring,
it might be that this additional interaction assists the transfer of
charge into molecular parts that are not directly connected with
OH group.
The HB formation is additionally confirmed after subtraction of
EB in C2Cl4 mixture from corresponding PH + EB in C2Cl4 mixture
which reveal additional vibrational feature in spectral range
2175–2025 cm1 most likely attributed to the C„C  OH HB com-
plex (Fig. 4b). The irregularity of the observed vibrational signature
that does not resemble to the common shape of vibrational bands
may be explained as follows: when subtracting binary from
12 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14

Fig. 4. IR spectra of EtOH + EB mixtures in C2Cl4 in spectral ranges: (a) 3680–3560 cm1 (OH and OH   stretching) after C2Cl4 subtraction in 1001.19 lm cell; (b) 2175–
2052 cm1 (C„C   stretching) after EB + C2Cl4 subtraction in 1001.19 lm cell; and (c) second derivative of the feature (C„C   stretching band) in (b). The initial
concentration of EtOH in these solutions was c0(PH) = 0.0069 mol dm1, while the initial concentration of EB was in range 0.19600 mol dm3 6 c0(EB) 6 0.90233 mol dm3.

ternary mixture IR spectrum, the differences between them, in
terms of their intensities, are rather small. In effect, we may expect
the feature that resembles more to the noise than to the physically
meaningful signal. However, since the obtained difference gener-
ates the band profile that becomes negative on the high-frequency
side of the expected band maximum and positive on the low-
frequency side, respectively (expected according to the binary mix-
ture), it may be concluded that at certain wavenumbers ternary
mixture is of greater intensity than binary, while at some other
wavenumbers the situation is opposite. The most simple explana-
tion for this phenomenon is simply the appearance of small but
non-negligible shift of the band maximum due to the small differ-
ences in the positions of the C„C and C„C   oscillators
(1–2 cm1). Thus, the position of the C„C   stretching band, being
the most important spectral parameter of interest, is further esti-
mated by employing derivative spectroscopy (see Supplementary
Materials). After taking second derivative of the spectral feature
(Fig. 4c), vibrational band was revealed that absorbs between
2114 and 2115 cm1. Small shift upon HB formation
ðDm~ ¼ 1—2 cm1 Þ is usually registered when weak HBs are con-
cerned [26]. The direction of the shift towards higher wavenum-
bers implies shortening of C„C bond of EB upon complexation
with EtOH (HB donor).
The comparison with the calculated IR spectra reveals an oppo-
site trend; two bands attributed to the stretching of associated
C„C moiety are expected and both are shifted to the lower wave-
numbers with respect to the monomer band, for Dm ~ ¼ 1 cm1
(structure 1a) and Dm ~ ¼ 5 cm1 (structure 2a). Since the second
one originates due to the complex in which HB is accomplished
directly via C„C group, this complex is presumably responsible
for the appearance of the observed phenomenon. In this example,
however, just as in the previous one, we are faced with the situa-
tion in which calculations predicted low-frequency shift of the
associated C„C oscillator, while in the reality the situation is
opposite. Aside to the possible causes like accounting for the expli-
cit solvation as already elaborated, it is also likely that the proper
inclusion of anharmonic effects may produce more accurate results
when the direction of the shift of C„C   oscillator is under
consideration.
Determination of the association constant
By employing expression (3) from Supplementary Materials
section, association constants of PH  EB HB complex in C2Cl4
obtained here are measured at 20 °C, and, respectively, 26 °C. The
values are Kc(20 ± 1 °C) = 0.54 ± 0.09 mol1 dm3 and, respectively,
 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14 13

Kc(26 ± 1 °C) = 0.36 ± 0.08 mol1 dm3 and are, as expected, classi- obtained by using IR–UV double resonance spectroscopy in gas
fied as weak HBs. The important implication of obtained Kc value phase coupled with calculations at B97-d/TZVPP and MP2/TZVPP
comes out when HB basicity of EB in term of Abraham’s bH 2 param- levels of theory, suggest that OH  p(C„C) interaction is responsi-
eter [37] is to be determined since, at present, bH 2 descriptor for any ble for a dimer formation. When the latter was studied in matrix
p system is unknown. Thus, from expression log K c ¼ isolation [42], however, experimental evidences indicate that,
H
7:354  aH H
2 b2  1:094, and knowing Abraham’s a2 parameter for aside OH  p(C„C) interaction, „CAH  O interaction operates
H
PH (0.596), it is estimated that b2 for EB is 0.14 ± 0.09 (from Kc in complexation. The former is indicated by the low-frequency
obtained at 26 ± 1 °C). It has to be emphasized that in EB basicity shift of OH stretching of PH when ethyne is present
designates overall p system (both C„C group and phenyl ring). (D  77 cm1), while the latter by the shift of „CAH stretching
Although high dilution method can be applied for determination band, when PH is present, for about 44 cm1 to the lower frequen-
of and , it functions by far better for medium strong HBs cies when compared the position when PH is absent. This example
than weak ones. Arnett et al. [38] shown that in weak HB com- also suggests high impact of the surroundings on the complexation
plexes with small Kc values, such as here, are also small; they pattern. Associations in which EB is HB acceptor are poorly charac-
are within range 4.2 kJ mol1 to 16.7 kJ mol1, while the accom- terized in terms of thermodynamics; the majority of qualitative
panied uncertainties can vary from ±1.7 kJ mol1 to ±2.1 kJ mol1. findings is, however, available in [26] and in the experimental
In turn, when the value of is near the lower limit of mentioned and calculated works by Naresh Patwari et al. [1–3,27,33,34].
range, as expected here, the uncertainty can vary 40% to 50% of the
measured value, indicating that the results obtained with this
method would not be very reliable. As an alternative to the high
Conclusions
dilution method in determination of , pure base method [38]
should be conducted, where the uncertainties are within the range
Hydrogen bonding between PH and EB in stoichiometry 1:1 is
0.4–0.8 kJ mol1. However, this method requires the dissolution of
characterized in term of association constant Kc. The values are
PH in pure EB, where EB  EB self-association, i.e. competitive reac-
determined at two temperatures, 20 °C and 26 °C and they are
tion to the PH  EB association, occurs, that is aimed to be avoided.
0.54 ± 0.09 mol1 dm3 and, respectively, 0.36 ± 0.08 mol1 dm3.
Since and values of PH  EB HB complex in CCl4 and,
The unambiguous participation of C„C group in HB is demon-
indirectly, Kc values, are already reported by Yoshida et al. [5]
strated by the appearance of C„C   stretching band. The absence
( (PH  C„C, PH  phenyl) = 3.8 kJ mol1, 6.9 kJ mol1;
of the shift of associated C„C oscillator, in comparison with unas-
(PH  C„C, PH  phenyl) = 21.3 J K1 mol1, 35.9 J K1 mol1;
sociated C„C oscillator upon complexation, is explained in the
Kc (PH  C„C, PH  phenyl) = 0.27 mol1dm3, 0.22 mol1dm3),
context of involvement of p  p interactions in HB complex. It is
they should be commented in the light of the present research:
proposed that C„C moiety, when is in HB complex, does not
(i) Yoshida’s results are based on the assumption that only PH  EB
shorten or lengthen because it interacts with both OH group and
dimers in stoichiometry 1:1 were formed. However, they worked
phenyl ring of PH. This geometry of the complex is enabled by rota-
at analytical concentrations at which PH very likely self-associates
tion of PH around the axis perpendicular to the plane formed by
(c0(PH) = 0.020 mol dm3). (ii) The absorption intensities of the
PH  EB HB complex. According to the ab initio calculations, the
bands attributed to the stretching of OH  p oscillators, as well
presumed arrangement of monomers has complexation
as their positions, were obtained by integration. Wherever integra-
energy DE = 19.9 kJ mol1, while the most stable complex
tion of several weak overlapping bands is to be made, there is
(DE = 26.7 kJ mol1) is the one whose arrangement not accompa-
enough space for rising up the uncertainties. This is also possible
nied by the proposed rotation.
in the discussed case, especially due to overlapping with neglected
The ultimate importance of p  p interactions is further con-
OH  O stretching bands. (iii) Absorption coefficients of the bands
firmed when IR spectra of EtOH + EB in C2Cl4 mixtures, where
bring additional unreliability in the analysis since they are esti-
p  p interactions are absent, are analyzed. In the latter, OH  C„C
mated from the correlation between frequency shifts and shift in
HB is certainly formed, as proven from the appearance of both
the absorption intensities [10].
OH   and C„C  stretching bands. Upon complexation, C„C  
As the Kc reflects overall stability of the complex and is, presum-
stretching band shifts to the higher wavenumber, as expected for
ably, the result of the interplay of OH  p and p  p interactions, it
functional group who acts only as HB acceptor. The comparison
is interesting to compare the stability of PH  EB HB complex with
of the C„C   stretching band positions in these two examples
other weak HB complexes where PH is HB donor, while HB accep-
show that, when additional driving force like p  p interactions,
tor is, in a certain fashion, similar enough to EB. In this light, com-
aside HB, is enabled, properties of molecules like bond length, even
parison with PH  benzene and PH  ethyne is the most useful for
in the weak associations, can be changed.
the estimation of the contribution of certain interaction type on
overall stability here studied complex. The value of determined
equilibrium constant is slightly greater than the one obtained from
Acknowledgements
PH  benzene in CCl4 [39] which is 0.26 mol1 dm3 at 298 K (25 °C)
which is considered as intermediate case of interplay of HB and
This work was supported by a Grant No. 0982904-2927 from
van der Waals dispersion forces. Calculations at B3LYP/6-
Ministry of Science, Education and Sport of the Republic of Croatia.
31+G(d,p) level predicted that, in gas phase, PH and benzene form
D.V. thanks to J. Alerić and T. Parlić-Risović from Croatian Metrol-
dimer in a way that OH group of PH points towards the bond
ogy Institute for measuring the densities of ethynylbenzene and
between adjacent C-atoms of benzene, in contrast to the expected
tetrachloroethene. M.V. acknowledges Croatian Academy of Sci-
direction to the center of p system [40]. As the planes of PH and
ences and Arts for financial support.
benzene molecule are perpendicular, the additional interaction of
one of the ortho H atoms of PH with the bond between adjacent
C-atoms opposite to the former pair is enabled. Slightly greater
Kc in PH  EB complex than in PH  benzene complex implies the Appendix A. Supplementary material
importance of ethyne moiety in overall stability of the former.
When PH  ethyne interaction is discussed, in spite of the lack of Supplementary data associated with this article can be found, in
the value of Kc, the most recent experimental findings [41], the online version, at http://dx.doi.org/10.1016/j.saa.2014.04.149.
14 D. Vojta, M. Vazdar / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 132 (2014) 6–14
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