Journal of Molecular Structure 1098 (2015) 26e33

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

The self-aggregation of some 7H-indolo[1,2-a]quinolinium dyes in

aqueous solution
Marta J. Sawicka

w Ave.
Department of Instrumental Analysis, Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology, Szczecin, Piasto
42, 71-065 Szczecin, Poland

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 28 November 2014
Received in revised form
13 May 2015
Accepted 13 May 2015
Available online 28 May 2015

The aggregation of some 7H-indolo[1,2-a]quinolinium dyes in aqueous solution was investigated based
on UVevis spectroscopy. The inuence of pH, dye concentration, ionic strength and the addition of
organic solvents on the process was studied. The aggregation took place in alkaline solution and was
strongly affected by ionic strength and the presence of organic solvents. The existence of aggregates in
the solution was manifested in a new band appearance which exhibited bathochromic shift with respect
to the monomer band. For all studied dyes the band was assigned to the dimer and the equilibrium
constants for dimer formation were calculated. The dye tendency to aggregate was determined by its
structure and was enhanced by the presence of naphthalene moiety in comparison to that of benzene
ring as well as electron-rich substituents such as halogens.
2015 Elsevier B.V. All rights reserved.

Keywords:
Merocyanine
Absorption spectra
Aggregate
Equilibrium constant
Ionic strength

1. Introduction
Some groups of dyes, such as cyanines, merocyanines or some
pyrylium or thiopyrylium laser dyes, tend to aggregate in concentrated or even in diluted solutions [1e3]. Aggregation affects their
colouristic and photo-physical properties and is therefore of special
interest due to its possible application in understanding and
interpretation of a great variety of problems, such as energy
transfer in biological systems, conformation of polypeptides,
staining properties of dyes for biological specimens. Moreover, the
phenomenon can be very useful for analytical application in optical
sensor, adsorption, and photography [4e6].
Many theories have been suggested to explain the forces of
attraction between ionic dyes in solution [7,8]. The aggregation
have been attributed to van der Waals forces, ion-dipole and
dipoleedipole interactions, and forces arising from delocalized pelectrons. The mutual repulsion forces are reduced by the inclusion
of counter ions [9]. According to previous studies, the dyeedye
interactions are not the major driving force behind the aggregation
but strong waterewater interactions force the dye to aggregate
[10]. The increase in the molecular size or the concentration of

E-mail address: msawicka@zut.edu.pl.

http://dx.doi.org/10.1016/j.molstruc.2015.05.032
0022-2860/ 2015 Elsevier B.V. All rights reserved.

solute leads to the destruction of the water network since the

number of water molecules is not big enough to form a complete
shell of hydration, especially when the dipole character of a dimer
is smaller than that of a monomer. In more concentrated solution,
the destruction of the shell of hydration facilitates the dyeedye
contact and the same the aggregate creation [11].
The UVevis absorption spectroscopy is one of the most suitable
methods for studies of the aggregation process since the aggregates
in solution usually exhibit distinct changes in the absorption
spectrum in comparison to the monomeric species. Quantitative
studies of aggregation properties of dyes are the most often conducted in the concentration range 10
3 e 10
6 mol L
1 in which
usually monomeredimer equilibrium exists. The values of aggregation constant determined for various dyes are of the order of
103e104 L mol
1 [2,4,5,8,12].
The aggregation behaviour of cyanine dyes has been studied
extensively since these are the best-known self-aggregating dyes
[13,14]. The structurally related dyes to cyanines are merocyanines. These are systems in which an electron-donating
group, D, is linked by a conjugated system, R, to an electronaccepting group, A. Their intermediate p-electronic structure of
a ground state can be described in terms of two mesomeric
structures DeReA 4 DeReA- differing in a charge distribution
and bonds' length, and as a consequence in a dipole moment and

M.J. Sawicka / Journal of Molecular Structure 1098 (2015) 26e33

solvent shell. The rst one is a quinoid form and the second e a
zwitterionic one (also named as betaine) [15]. Among the merocyanines, 7H-indolo[1,2-a]quinolinium dyes are worth
mentioning [16e22]. They are usually generated in situ from
perchlorates of corresponding hydroxyaryl compounds via treating them with anhydrous potassium carbonate. These merocyanines exhibit distinct solvatochromic properties, which
means that their UVevis absorption spectra strongly depend on
the polarity of the medium. Therefore, they have found many
applications, for instance in the determination of the ternary
solvent mixtures composition [23,24], in investigations of the
diffusion prole in polymers [25,26], as well as in quantitative
analysis of ionic surfactants [27e30]. These investigations concerned their monomeric forms.
In this paper the aggregation behaviour of some 7H-indolo[1,2a]quinolinium merocyanines in alkaline aqueous solutions is
described for the rst time. The dyes used in the study were: 5-(4hydroxyphenyl)-7,7-dimethyl-7H-indolo[1,2-a]quinolinium
perchlorate (IQHH), 5-(3-bromo-4-hydroxyphenyl)-7,7-dimethyl7H-indolo[1,2-a]quinolinium perchlorate (IQBH), 5-(3,5-dibromo4-hydroxyphenyl)-7,7-dimethyl-7H-indolo[1,2-a]quinolinium
perchlorate (IQBB), 5-(6-hydroxynaphthyl-2)-7,7-dimethyl-7Hindolo[1,2-a]quinolinium perchlorate (IQNH) and 5-(5-bromo-6hydroxynaphthyl-2)-7,7-dimethyl-7H-indolo[1,2-a]quinolinium
perchlorate (IQNB). The structures of these dyes are depicted in
Scheme 1. Aggregation was studied by UVevis absorption spectroscopy. The inuence of dye concentration, pH of the solution,
ionic strength and the addition of an organic solvent on the formation of aggregates was analysed.
2. Materials and methods
2.1. Materials
The 7H-indolo[1,2-a]quinolinium dyes were synthesised according to the method described in the literature [16e19]. NaOH
and NaCl were purchased from ChemLand. DMSO for spectroscopy,
methanol and DMF analytical grade were purchased from POCh
(Gliwice). Distilled water was generated in glass Bchi apparatus
and was used without additional purication.
2.2. Spectrophotometric measurements
UVevis absorption spectra were recorded with computercontrolled spectrophotometer Specord M40 (Carl Zeiss Jena, Germany) modied by Medson Electronics, Co Ltd., in the
12,000e27,000 cm
1 range at temperature 25 0.1  C. Gas-tight
quartz cells with 5 cm, 1 cm and 0.1 cm path length were used.
The concentration-dependence measurements: dye solutions

27

(1.06$10
5 e 2.12$10
4 mol L
1) were prepared by adding appropriate amount of the dye concentrate (15 mg of the dye in the form
of perchlorate and 0.75 mL of anhydrous DMSO) to the 0.02%, 2%
and 8% w/w NaOH solution (pH 11.5, 13.5 and 13.9), respectively, at
constant concentration of DMSO (0.74% v/v). It was checked that
the inuence of this amount of DMSO on the shape and the position
of absorption bands corresponding to monomer and aggregate
does not exceed the instrumental error.
The measurements of the organic solvent effect: to 2 mL of IQNB
solution (8.82$10
5 mol L
1) in 2% NaOH: 25, 50, 100, 150, 225 and
300 mL of methanol or DMF were added. After each step of the
organic solvent addition, the absorption spectra were measured.
Additionally, the same amounts of water were added to the dye
solution. Since the shape of the absorption band did not change and
its position was shifted less than 200 cm
1, it was concluded that
the dilution of the alkaline dye solution could not be the reason of
the observed spectral changes.
The measurements of the ionic strength inuence: the dye solution
(0.05 g L
1) in water containing 0.02% NaOH was mixed with the
dye solution (0.05 g L
1) in NaCl solution (3.62 mol L
1) containing
0.02% NaOH in the ratio: 1:0, 3:1, 1:1, 1:3 and 0:1.

3. Results and discussion

3.1. The effect of the dye concentration
UVevis spectra of aqueous solution of IQNB were measured in
concentration range 1.06$10
5 e 2.12$10
4 mol L
1 at four pH
values. The sample spectra are shown in Fig. 1aec. At pH 5.5, the
dye exists in the solution as a salt (perchlorate) since this pH value
is below the pKa of the dye which equals to 7.27 [19]. The band
corresponding to perchlorate is located at 24,721 cm
1 (spectra not
shown). In this case any spectral changes with increasing dye
concentration cannot be observed. After pH exceeds the pKa value
of the dye dissociation of hydroxyl group occurs and the dye exists
as a merocyanine. In UVevis spectrum the band corresponding to
salt disappears and the new band appears at 20,904 cm
1. At pH
11.5, the band attributed to merocyanine fulls the LamberteBeer
law up to concentration 3.17$10
5 mol L
1. Therefore, one can
admit the dye exists as a monomer. However, the further increase
in the dye concentration leads to a slight bathochromic (red) shift
(Fig. 1a).
At pH 13.5 the increase in the dye concentration causes a
distinct red shift (Fig. 1b). It results from the decrease in the intensity of the monomer band (the band at 20,904 cm
1) which is
accompanied by the rise in the intensity of the new low-energy
band (the band at 18,408 cm
1). Since the new band appears as
the concentration of the dye increases it can be attributed to the
aggregate. If the solution is even more alkaline (at pH 13.9), the

Scheme 1. The structures of 7H-indolo[1,2-a]quinolinium dyes.

28

M.J. Sawicka / Journal of Molecular Structure 1098 (2015) 26e33

[15]) were added to IQNB aqueous solution at pH 13.5 and the

spectral changes were investigated.
As it can be seen in Fig. 3, the addition of the organic solvent
induces the hypsochromic (blue) shift of the absorption band
resulted from the rise of the intensity of the band attributed to
monomeric merocyanine. Since it is known that organic solvents
hinder aggregation, this experiment can conrm that the observed
spectral changes result from the aggregation/disaggregation
phenomenon.
3.3. Determination of equilibrium constant
The observed spectral changes i.e. the decrease in the intensity
of the monomer band accompanied with the rise in intensity of the
new band which are easy to noticed with increasing dye concentration as well as the increase in intensity of the monomer band
after organic solvent addition are typical for aggregates. It allows
the obtained results to be analysed in terms of equilibrium between
monomer and aggregate form of the dye.
According to the reaction scheme:

aM/Aa

(1)

where M, Aa and a denote monomer, aggregate and the number of

monomer units in aggregate, respectively, the equilibrium constant
K can be calculate as follows:

Aa 
Ma

(2)

Due to the fact that the concentrations of monomer [M] and

aggregate [Aa] are related with the total concentration of the dye
[D] according to the equation:
Fig. 1. Absorption spectra of IQNB measured at pH 11.5 (a), 13.5 (b) and 13.9 (c),
respectively; dye concentrations: 1.76$10
5 mol L
1 (1), 8.82$10
5 mol L
1 (2),
8.82$10
4 mol L
1 (3); path length: 5 cm (1), 1 cm (2), 0.1 cm (3).

band in long-wave part of the spectrum is a dominant one which

proves that the concentration of the merocyanine in form of
monomer is really low even in diluted dye solution (Fig. 1c).
The further increase in either dye concentration or pH value leads
to the appearance of precipitate which can be noticed in UVevis
spectrum as the rise of the base line and decrease in the intensity of
the absorption band. To check if the precipitate contains dye aggregates only, the concentrated dye solution (9.95$10
4 mol L
1) in
20% NaOH was centrifuged, the solution was decanted, and the
residue was gradually re-dissolved in water. The recorded UVevis
absorption spectra of the solutions obtained do not demonstrate any
changes in comparison with the spectra described above.
The electronic absorption spectra were measured of aqueous
solutions of IQNH, IQBB, IQBH and IQHH, respectively, at pH 11.5,
13.5 and 13.9 at increasing dye concentration (1.6$10
5 e
2$10
4 mol L
1). The sample spectra at pH 11.5 and 13.9 are shown
in Fig. 2aed. It is evident that the spectral changes are not identical
in case of all studied dyes. IQNH fulls the LamberteBeer law in the
whole studied concentration range at pH 11.5, whereas the aggregation is observed at pH 13.5 and 13.9. In the spectra of IQBB and
IQBH the low-energetic band corresponding to aggregate formation
appeared at pH 13.9 only. In case of IQHH the changes are the least
evident at any pH values.

D M aAa 

(3)

the concentration of the aggregate can be expressed as follows:

Aa 

D
M
a

(4)

Introduction of the Equation (4) into the Equation (2) and its
rearrangement into the logarithm form leads to the linear functions
obtaining:

log K logD
M
log a
a logM

(5)

and

logD
M a logM const

(6)

From the slope of the plot described by the Equation (6) it is

possible to evaluate the a value which enable the equilibrium
constant to be calculated as well.
The concentrations of the monomer being in the equilibrium
with the aggregate at different total dye concentrations could not
be calculated from LamberteBeer law in case of all studied compounds since the absorption bands attributed to the monomer and
the aggregate, respectively, are partially overlapped. Assuming that
only two forms (the monomer and one type of aggregate) exist in
the solution, the calculations of the concentration of particular
species can be done according to the equation:

3.2. The inuence of organic solvent

An
M$Mn Aa $Aa
n
l

For studying the effect of organic solvents two solvents differing

in polarity i.e. methanol (ETN 0:762 [15]) and DMF (ETN 0:404

where An is the absorbance value at a given wavelength n, Mn is the

molar extinction coefcients of the monomer at the wavelength n,

(7)

M.J. Sawicka / Journal of Molecular Structure 1098 (2015) 26e33

29

Fig. 2. UV-vis spectra of IQNH (a), IQBB (b), IQBH (c) and IQHH (d) measured at pH 11.5 (dotted line) and 13.9 (solid line), respectively; dye concentrations (mol L
1): 2$10
5 (1),
5$10
5 (2), 8$10
5 (3), 1.2$10
4 (4); path length: 1 cm.

and Aa is the molar extinction coefcients of the aggregate at the

n
wavelength n and l is the thickness of analyzed layer (path length).
Mn values for each studied dye are available from the spectra
measured at pH 11.5 for diluted dye solution (the dyes' concentration amounts to 2$10
5 mol L
1). In this case only monomeric
form of the merocyanine is present in the solution and its concentration [M] is equal to the total dye concentration [D]. On the
other hand, in concentrated dye solution at pH 13.5 the aggregate is
assumed to be the only form of IQNB, IQNH, IQBB and IQBH merocyanines ([M] 0). However, the Aa cannot be calculated from
n
the UV-VIS spectra due to both the a value and as a consequence
[Aa] are unknown. Therefore, an apparent molar extinction coefcients of the aggregate *Aa was introduced which was calculated
n

Fig. 3. UVevis spectra of IQNB (8.82$10
5 mol L
1) measured in 2% NaOH e methanol
(a) and 2% NaOH e DMF (b) mixture; organic solvent concentration (% v/v): 0 (1), 1.23
(2), 2.44 (3), 4.76 (4), 6.98 (5), 10.11 (6), 13.04 (7).

from the spectra recorded at pH 13.9 and [D] equals to

2$10
4 mol L
1 as follows:

*Aa
n

An
D

(8)

and the Equation (7) was rearranged into the form:

An
M$Mn X$*Aa
n
l

(9)

where X$*Aa Aa $Aa , X a$Aa  and *Aa Aa =a.

n

According to Equation (9) the concentration of the monomer

[M] at different total dye concentrations [D] were determined by
multiple regression analysis. The calculations were done based on
the spectra recorded at pH 11.5 for IQNB, at pH 13.5 for IQNB, IQNH
and at pH 13.9 for IQNB, IQNH, IQBB, IQBH. The concentrations of
the monomer were determined with high accuracy. The values of
correlation coefcients exceed 0.999 (or more) and the values of
standard deviations calculated in absorbance unit were 3.5$10
3 (or
less). The evaluated values of [M] were applied into the Equation (6)
and plots describing log([D]
[M]) as a function of log[M] were
created. The results obtained at pH 13.9 are presented in Fig. 4.
The obtained plots, for each case, follow the straight line with
the correlation coefcient r at least 0.97 and the slope amounts to
2.0 0.1. Therefore, one can admit that the band in the long-wave
part of the UV-VIS spectrum of all studied dyes can be assigned to

Fig. 4. Determination of the number of monomer units in aggregate a at pH 13.9 for

IQNB (rhombuses), IQNH (squares), IQBB (triangles), IQBH (cycles).

30

M.J. Sawicka / Journal of Molecular Structure 1098 (2015) 26e33

the dimer. The equilibrium constants for dimer formation (the

dimerisation constant) which were calculated from the equation:

D
M
2
2

(10)

M

are collected in Table 1.

3.4. The ionic strength inuence
The aggregate formation was found in aqueous solutions of
studied dyes at high pH value, especially at pH 13.5e13.9. So small
differences in the pH were induced by signicant increase in NaOH
concentration (from 2% to 8% w/w) which leads to the increase in
ionic strength of the solution as well. To establish whether OH

anions are required to aggregate formation or the aggregation is
induced by the increase in the ionic strength of the solution, electronic absorption spectra were measured of IQNB and IQBB solutions, respectively, as a function of NaCl concentration at pH 11.5
(Fig. 5).
In both cases, the new band appeared the intensity of which
rose with increasing salt concentration. It proves that the ionic
strength induces the dye aggregation, making the water lattice
more rigid. Moreover, this tendency as well as the rise of the base
line in UVevis spectrum additionally conrm the fact that the
observed spectral changes are caused by the creation of
aggregates.
It is well known that water molecules create ordered structures.
The structure of liquid water has been intensively investigated, and
most models of water can be partitioned into two broad categories:
(a) mixture models and (b) distorted hydrogen bond or continuum
models [31,32]. The mixture models postulate the simultaneous
existence of two distinct types of structures. In the continuum
models, liquid water comprises a random, three-dimensional
network of hydrogen bonds encompassing a broad distribution of
OeH/O hydrogen bond (HB) angles and distances, but the water
networks cannot be broken or separated into distinct molecular
species as in the mixture models. Many studies proved that in binary water e organic solvent mixture in water-rich region the
water molecules tend to prefer the interactions between themselves via hydrogen bond than with molecules of other species [33].
The small contaminants are closed in a sphere consists of about 24
molecules of water [34]. The studies of Marcus [35,36] had
demonstrated that some co-solvents does enhance the internal
water structure in water-rich region of the mixture whereas other,
many of which are strongly hydrogen bonded with water, does not.
Chandra [37] found a reduction in the number of H-bonds with
increasing concentration of ions (NaCl and KCl), indicating that
water molecules are signicantly inuenced by the presence of
ions. Suresh with co-workers [38] concluded that it can result from
the steric hindrance of the ion or due to the high dipole ordering by
the ionic eld.
In case of the studied merocyanines, at low ionic strength the
monomer is the only form of the dye or the strongly predominant

one. It indicates that the solvation by water takes place of small ions
as well as of the dye molecules. Since the merocyanine competes
against other ions for water molecules, the increase in NaOH or
NaCl concentration leads to the reduction of dyeewater interactions. As a consequence, in the solution of high ionic strength
the dye molecule tends to interact with other dye molecule rather
than with water, thus the aggregates appear.
Therefore, the pH value as high as 13.5e13.9 seems to be not
necessary to aggregate formation, but the high concentration of
ions favours the aggregation. The formation of aggregate is possible
at pH higher than pKa of the dye which enable the whole population of the dye exists in the form of zwitterionic merocyanine. The
lack of zwitterionic form in case of hydroxyaryl perchlorate hinders
the formation of the stable aggregates. It is well known that pH
value strongly inuences the aggregation tendency of other dyes,
especially if they have a substituent such as amine or hydroxyl
group which can be protonated or undergo dissociation at different
pH values [39e41]. The tendency to aggregate of merocyanine (at
pH higher than pKa) and the lack of it in case of hydroxyaryl
perchlorate (at pH lower than pKa) suggests that electrostatic interactions play an important role in aggregate formation. These
interactions concern the ionized hydroxyl group and the indoloquinolinium moiety with positive charge at nitrogen atom. For that
reason it can be assumed that merocyanine molecules in aggregate
are antiparallel stacked which enables the part of the merocyanine
molecule with the positive charge to face the part of the molecule
with the opposite one.
The changes in UVevis absorption spectra which are observed
in the solution of aggregating dyes are the most often interpreted
based on the Kasha exciton theory [42,43]. According to this theory,
two type of aggregates are distinguished: face-to-face H-aggregates
with the absorption band blue shifted in comparison to the band
attributed to monomer and face-to-tail J-aggregates with the red
shifted aggregate band. It is agreed that both H- and J-aggregates
are composed of parallel dye molecules but they differ one from
another in the slip angles i.e. angle between the line of centres of a
column of dye molecules and the long axis of any one of the parallel
molecules. A small slip angle is attributed to the J aggregates and a
large slip angle e to the H aggregates [13,44]. Merocyanine dyes
preferentially form face-to-face-stacked centrosymmetric H-type
dimers [44,45]. It is possible due to almost planar structure of a dye
in which a donor (acceptor) part of one molecule is located directly
under an acceptor (donor) part of the other molecule. Nevertheless,
examples of J-aggregating merocyanines have been also described
especially in LB lms [46] as well as in the solution [44,47e50] with
a slip of one molecule against each other along the direction of the
long molecular axis.
Since in case of the studied dyes red shift of absorption band
during aggregation is observed the antiparallel stacking of two
molecules in dimer seems to be quite probable.
Besides H and J aggregates theory the observed spectral shifts
can be related to the structure of a dimer taking into account the
changes of the molecule dipole moment occurring during aggregation as well as the soluteesolvent interactions. Both factors

Table 1
Aggregation characteristic of studied dyes at different pH value.
pH

11.5

13.5

dye

IQNB

IQNB

IQNH

IQNB

IQNH

IQBB

IQBH

a
r
na
K (L mol
1)

2.04
0.979
6
947

1.97
0.996
7
3836

1.94
0.998
7
932

1.91
0.979
6
1.67$105

2.03
0.970
6
1.22$105

1.92
0.995
8
2.25$104

1.90
0.999
7
1.47$104

The number of experimental points.

13.9

M.J. Sawicka / Journal of Molecular Structure 1098 (2015) 26e33

31

Fig. 5. UVevis spectra of IQNB (a) and IQBB (b) (0.05 g L
1) in NaCl solutions; NaCl concentration (mol L
1): 0.00 (1), 0.90 (2), 1.81 (3), 2.71 (4), 3.62 (5).

determine the excitation energy and are especially important in

case of the dyes which exhibit solvatochromic properties.
The solvatochromic dyes are compounds with electric dipole
moment in a ground state distinctly different from that in an
excited state. In that case, the polarity of the medium affects the
position and the shape of UV-VIS absorption bands. The extent and
the direction of these changes, with increasing solvent polarity, are
determined by the dipole moments of the ground and excited
states. The more polar excited state provides stronger interaction
with polar solvent which leads to the bathochromic shift (positive
solvatochromism). And analogously, when a polar ground state is
stronger stabilised by the polar medium, the hypsochromic shift of
the absorption band is observed (negative solvatochromism) [15].
All of the studied merocyanines exhibit negative solvatochromism in polar solvents as well as in solvents of medium
polarity [18,20,22]. It means that they dipole moment in a ground
state is greater than that in an excited state. The interactions between the monomeric polar zwitterionic merocyanine and a polar
solvent (such as water) diminish the energy of the ground state
which results in the increase in the excitation energy (Scheme 2).
During the dimerization, the antiparallel stacking of the molecules
leads to the compensation of their dipole moments. Therefore, a
dimer form is much less polar than monomer which causes weaker
interaction with polar solvent. As a consequence, the transition
energy diminishes and the absorption band attributed to the dimer
is red shifted in relation to the one corresponding to monomer.
Furthermore, the decrease in the dipole moment of the molecules during aggregation seems to be also the reason why organic
solvents hinder aggregation. As it can be seen in Fig. 3, the addition
of DMF results in the spectral changes which are more evident than
these caused by more polar methanol. According to Yazdani et al.

Scheme 2. Changes in excitation energy versus solvent polarity for monomer (DEM )
and dimer (DEA2 ). E0i is the ground state energy of monomer (M) and dimer (A2), and
E1i is the excited state energy of monomer (M) and dimer (A2), respectively.

[4] the dominant role of water as the most favourable solvent to

aggregation of ionic dyes is associated with its high dielectric
constant which reduces the repulsive forces between dye molecules in the aggregate. Thus, the dye molecules prefer to interact
with themselves rather than with the molecules of water. On the
other hand, in case of studied dyes the charge compensation of
monomers which occurs during aggregation allows the aggregates
to be solvated by less polar solvent. It makes the interactions between monomers weaker. As a consequence, aggregates break up
and the monomeric molecules appear in the solution again. It implies that hydrophobic forces play an important role in aggregation
of the studied dye as well.
3.5. The effect of the dye structure
The dyes used in these studies can be arranged in terms of their
tendency to aggregate formation as follows: IQNB > IQNH >
IQBB > IQBH > IQHH. Indeed, in the same series one can roughly
ordered the expected hydrophobic character of the dyes but some
other factors have to be taken into account as well. One can admit
that the dye ability to aggregate depends on the dye structure as
well as the type of substituents. During the aggregation the
substituted or unsubstituted phenyl ring or naphthalene moiety
faces the indoloquinolinium part of the dye. The factors which
facilitate the interactions between these two parts of molecule,
such as pep interactions, will enhance the aggregation ability.
Therefore, the presence of naphthalene moiety favours aggregation
due to greater area of pep interactions in comparison with the dyes
with phenyl ring. This is the reason why the dyes with naphthalene
moiety exhibit the greatest tendency to aggregate.
The comparison of the spectra of IQNB and IQNH as well as IQBB
and IQBH or IQHH indicates that the aggregation is enhanced also
by the electron-rich substituents such as halogens. Apart from the
fact that halogens increases the hydrophobic part of the monomer
molecule, they can interact with p electrons of indoloquinolinium
moiety via halogen bond providing the stabilization of the forming
aggregate. The importance of the CeXep interactions in crystal
structures was noticed by Bishop et al. who described the X-ray
structures of many inclusion compounds [51e54]. According to
studies of Mafud and co-workers [55], the CeXep interactions are
one of three types of interactions which enhance crystal packing of
trans-1,2-dibromo-2-styrylpyridine. Moreover, Swierczynski and
co-workers found a large number of fragments involved in noncovalent interactions of aryl components with halogens in the
Cambridge Structural Database (CSD) [56]. Theoretical and experimental analyses have shown that the electron density around a
bonded halogen atom is not spherically but anisotropically
distributed: negative charge is concentrated in the equatorial area
(i.e. perpendicular to the CeX axis) and positive charge along the
CeX bond, which is called s-hole. This effect, known as polar
attening, is strongly enhanced by the presence of electron

32

M.J. Sawicka / Journal of Molecular Structure 1098 (2015) 26e33

withdrawing groups and also increasing in the order Cl < Br < I

[57,58]. Therefore, it can be expected that the halogen bond is
especially strong in case of IQBB which, in fact, forms the aggregates
the most readily in comparison to the rest of merocyanines with
phenyl ring. The presence of phenyl ring without any additional
substituents can be the reason that IQHH exhibits the lowest aggregation tendency.
Based on the assumption that monomer molecules are antiparallel stacked in aggregate there are a few possible structures of
the dimer. Some of them are presented in Scheme 3. One of the
factors which inuence the number of the possible structures is the
mutual arrangement of the indoloquinolinium parts of two
monomer molecules in dimer. As a result various structures exist
which can be named syn and anti dimers differing in p e
peoverlapping and the distance between ionized hydroxyl group
with negative charge and the nitrogen atom with positive one.
Moreover, due to the possibility of the free rotation around the
single bond between indoloquinolinium part and benzene or
naphthalene moiety s-cis and s-trans rotamers can be considered as
well. In the solution, the probability of the existence of each of
these structures seems to be similar. However, taking into account
electrostatic interactions, p e peoverlapping and CeXep interactions which inuences the stability of forming aggregates one
can assumed that the anti dimer composed of two s-trans
monomers is the most probable one. An attempt to conrm if this
dimer structure really dominates in the solution failed. The unsuccessful separation of a single crystal of the dimer made impossible the application of X-ray crystallography which is usually used
to the structure determination.

4. Conclusion
The aggregation of some 7H-indolo[1,2-a]quinolinium merocyanines is reported. It was found that the phenomenon is
strongly affected by ionic strength and the presence of organic
solvents. Electrostatic interactions, as well as hydrophobic forces
play an important role in aggregate formation. Merocyanine is the
only form of the studied dyes which can create the aggregates,
especially at high ionic strength. The dye tendency to aggregate is
determined by its structure. p e p interactions and CeXep interactions provide a stabilization of the forming aggregates.

Scheme 3. Schematic representation of the possible structures of dimer.

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