Solvent influence upon complex formation between different 1,8-dioxo-octahydroxanthene derivatives and yttrium(III) cation in some non-aqueous solvents using conductometric method

Article abstract of DOI:10.1134/S0036023616020029

The complexation reactions between the yttrium(III) cation and (4-chlorophenyl, phenyl, 4-nitrophenyl, 4-methoxyphenyl, 4-methylphenyl) 9-substituted 1,8-dioxo-octahydroxanthene were studied in acetonitrile (AN) and methanol (MeOH) at different temperatur

Full text of DOI:10.1134/S0036023616020029

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2016, Vol. 61, No. 2, pp. 250–256. © Pleiades Publishing, Ltd., 2016.
PHYSICAL CHEMISTRY
OF SOLUTIONS
Solvent Influence upon Complex Formation between Different
1,8-Dioxo-octahydroxanthene Derivatives and Yttrium(III) Cation
in Some Non-Aqueous Solvents Using Conductometric Method1
S. Basafaa, A. Davoodniaa, N. Asefifeyzabadib, H. Sharifi Noghabib, and G. H. Rounaghib
aDepartment of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran
bDepartment of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
e-mail: ghrounaghi@yahoo.com; ronaghi@um.ac.ir
Received April 20, 2015
Abstract—The complexation reactions between the yttrium(III) cation and (4-chlorophenyl, phenyl, 4-nitro-
phenyl, 4-methoxyphenyl, 4-methylphenyl) 9-substituted 1,8-dioxo-octahydroxanthene were studied in ace-
tonitrile (AN) and methanol (MeOH) at different temperatures using the electrical conductivity measure-
ments. The conductance data show that the stoichiometry of all formed complexes between the Y3+ cation
and the studied ligands is 1 : 1 [ML]. The order of stability of the complexes formed between the organic
ligands and Y3+ cation in pure MeOH at 45°C was found to be: (3,6,6-Tetramethyl-9-(4-chlorophenyl)-1,8-
dioxo-octahydroxanthene·Y3+) > (3,6,6-Tetramethyl-9-(4-methoxyphenyl)-1,8-dioxo-octahydroxanthene ·
Y3+) > (3,6,6-Tetramethyl-9-(4-phenyl)-1,8-dioxo-octahydroxanthene·Y3+) ≈ (3,6,6-Tetramethyl-9-(4-
nitrophenyl)-1,8-dioxo-octahydroxanthene·Y3+)
>
(3,6,6-Tetramethyl-9-(4-methylphenyl)-1,8-dioxo-
octahydroxanthene·Y3+). The values of the standard thermodynamic parameters (
°
°
) for formation
ΔHc , ΔSc
of the complexes were obtained from temperature dependence of the formation constants of the complexes
using the van’t Hoff plots. The experimental results show that the thermodynamics of the complexation reac-
tions is influenced by the nature of solvent system and in most cases, the complexes are entropy stabilized.
Keywords: Y3+ cation, 1,8-dioxo-octahydroxanthene derivatives, acetonitrile, methanol conductometery
DOI: 10.1134/S0036023616020029
knowledge, there is no experimental data for the com-
plexation reactions between xanthene’s derivatives
and the metal cations in solutions.
Xanthene and its derivatives are an important class
of heterocyclic compounds. These compounds have
aroused a great interest due to the variety of biological
and therapeutic properties such as: anti-bacterials,
antioxidant, antifungal, antiviral, anti-inflammatory,
anti-depressants, anti-malarial, photodynamic ther-
apy and antagonists for the paralyzing action of zoxaz-
olamine [1–7]. Furthermore, these compounds are
utilized in material science as leuco-dye [8], in laser
technology [9], as pH sensitive fluorescent materials
for the visualization of biomolecular assemblies [10]
and as rigid carbon skeletons for the construction of
chiral bidentate phosphine ligands in catalytic pro-
cesses [11]. Because of the vital role of the heavy metal
cations in biological systems and also in industrial, the
study of the complexes of these metal cations with
such organic ligands is important [12]. Numerous
thermodynamic studies have been carried out upon
complexation processes between the macromolecule
organic ligands and various metal cations using differ-
ent experimental techniques [13], but to the best of our
The complex formation between the macromole-
cule ligands and the metal cations has been studied by
various physico-chemical techniques such as: spectro-
photometry [14], NMR spectrometry [15], polarogra-
phy [16, 17], potentiometry [18] and conductometry
[19]. Among these methods, the conductometry has
been considered as a sensitive and inexpensive method
with a simple experimental arrangement. In addition,
the measurements can be carried out at low solution
concentrations, where the interactions between the
cations and anions are known to be small [20]. Studies
of different complexes in various aqueous and non-
aqueous solvents show that the thermodynamic and
kinetic parameters for complexation processes and
even the stoichiometry of the complexes are affected
by the nature and composition of the solvent system
[21, 22].
In the present work, we studied the complex for-
mation between five different derivatives of xanthenes:
3,3,6,6-Tetramethyl-9-(phenyl)-1,8-dioxo-octahydrox-
1
The article is published in the original.
250

SOLVENT INFLUENCE UPON COMPLEX
anthene (C23H26O3) (Scheme 1), 3,3,6,6-Tetramethyl-
251
NO2
9-(4-methoxyphenyl)-1,8-dioxo-octahydroxanthene
(C24H28O4) (Scheme 2), 3,3,6,6-tetramethyl-9-(4-
chlorophenyl)-1,8-dioxo-octahydroxanthene (C23H25ClO3)
(Scheme 3), 3,3,6,6-Tetramethyl-9-(4-nitrophenyl)-
1,8-dioxo-octahydroxanthene (C23H25NO5) (Scheme 4)
O
O
and
3,3,6,6-Tetramethyl-9-(4-methylphenyl)-1,8-
dioxo-octahydroxanthene (C24H28O3) (Scheme 5)
O
and Y3+ metal cation at different temperatures in pure
AN and MeOH solvents using theconductometric
method.
Scheme 4. Structure of C23H25NO5.
CH3
O
O
O
O
O
O
Scheme 1. Structure of C23H26O3.
Scheme 5. Structure of C24H28O3.
OCH3
EXPERIMENTAL
Materials
O
O
Y(NO3)3 · 6H2O was purchased from Merck chem-
ical company and was used without purification. Ace-
tonitrile and methanol both from Merck company
were used with the highest purity and the organic
ligands were synthesized.
O
Scheme 2. Structure of C24H28O4.
Cl
General Experimental Procedure for Synthesis of the
Ligands
The aldehyde (2.0 mmole), 5,5-dimethyl-1,3-
cyclohexanedione (4.0 mmole) and diacetoxyiodo-
benzene (5 mol %) were mixed in water (10 mL) at
room temperature. The mixture was refluxed for the
times which are given in Table 1. Completion of the
reaction was monitored by TLC (Hexane : EtOAc 8 : 2).
After completion of the reaction, the mixture was
O
O
O
Scheme 3. Structure of C23H25ClO3.
Table 1. Synthesis of 9-aryl substituted 1,8-dioxo-octahydroxanthenes in aqueous media
O
Ar
O
O
Producta
Entry
Ar
Time, min
Yield, %
mp, °C
1
2
3
4
5
C6H5-
3a
3b
3c
3d
3e
30
60
94
90
89
94
91
196–198
150–152
210–212
222
4-MeOC6H4-
4-ClC6H4-
60
4-NO2-C6H4
4-MeC6H4
180
210
217–218
a
1
All the products were well characterized by H NMR and IR spectral data.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 61 No. 2 2016

252
BASAFA et al.
cooled to room temperature and the solid product was
filtered off and dried. The purity of the ligands was
checked by TLC and all these organic compounds
gave satisfactory spectroscopic data.
190
180
170
15˚C
25˚C
35˚C
45˚C
160
150
3,3,6,6-Tetramethyl-9-phenyl-1,8-dioxo-octahy-
droxanthene (3a). White solid, mp: 196–198°C, IR
(KBr) (νmax): 3350, 2980, 1795, 1725, 1699, 1640,
140
130
120
110
1520, 1360, 1345, 1260, 1233, 1201, 1195, 850, 843 cm–1.
1H NMR (CDCl3): δH 300 MHz 1.09 (s, 6H), 1.23
(s, 6H), 2.27–2.49 (m, 8H), 5.54 (s, 1H), 7.08–7.28
(m, 5H) (Scheme 1).
0
1
2
3
4
5
6
[L]t/[M]t
3,3,6,6-Tetramethyl-9-(4-methoxyphenyl)-1,8-
dioxo-octahydroxanthene (3b). White solid, mp: 210–
212°C, IR (KBr) (νmax): 3025, 2980, 1685, 1660, 1620,
1513, 1450, 1375, 1360, 1260, 1235, 1170, 1142, 1032,
1003, 840 cm–1.
1H NMR (CDCl3): δH 300 MHz 1.09(s, 6H),
1.22(s, 6H), 2.33–2.63 (m, 8H), 3.76 (s, 3H), 5.48 (s,
1H), 6.82 (d, 2H), 7.01 (d, 2H) (Scheme 2).
Fig. 1. Molar conductance versus mole ratio plots for
(3,6,6-Tetramethyl-9-(4-chlorophenyl)-1,8-dioxo-octa-
3+
hydroxanthene·Y ) complex in MeOH at different tem-
peratures.
Method
The experimental procedure to obtain the forma-
tion constants of the complexes was as follow: 20 mL
of Y(NO3)3 · 6H2O (1.00 × 10–4 M) solution was
placed in a titration cell and the conductance of the
solution was measured. Then a step-by-step increase
in the studied ligands solutions prepared in the same
solvent (2.00 × 10–3 M) was carried out by a rapid
transfer to the titration cell using a pre-calibrated
microburette and the conductance of a resulted solu-
tion was measured after each transfer at the desired
temperature. This addition continued until the total
concentration of the ligand was approximately five
times higher than the total concentration of the stud-
ied metal ion. The titration curves were thus obtained
in the form of the molar conductivity as function of
the ligand to metalcation molar ratio.
3,3,6,6-Tetramethyl-9-(4-chlorophenyl)-1,8-dioxo-
octahydroxanthene (3c). White solid, mp: 150–152°C,
IR (KBr) (νmax): 3028, 2980, 1680, 1660, 1620, 1490,
1480, 1360, 1200, 1170, 1140, 1090, 1010, 1000, 850,
840 cm–1.
1H NMR (CDCl3): δH 300 MHz 1.12 (s, 6H), 1.27
(s, 6H), 2.33–2.49 (m, 8H), 5.54 (s, 1H), 7.01 (dd,
2H), 7.26 (dd, 2H) [23] (Scheme 3).
3,3,6,6-Tetramethyl-9-(4-nitrophenyl)-1,8-dioxo-
octahydroxanthene (3d). White solid, mp: 222°C; IR
(KBr) (νmax) 3031, 2959, 1665, 1460, 1361, 1200, 1170,
855 cm–1.
1H NMR (DMSO-d6) δH 400 MHz 1.00 (s, 6H),
1.12 (s, 6H), 2.16 (dd, 4H), 2.41 (s, 4H), 4.46 (s, 1H),
7.50–7.63 (m, 2H), 8.06–8.16 (m, 2H) (Scheme 4).
3,3,6,6-Tetramethyl-9-(4-methylphenyl)-1,8-dioxo-
octahydroxanthene (3e). White solid, mp: 217–218°C;
IR (KBr) (νmax) 3020, 2960, 1661, 1465, 1365, 1205,
RESULTS AND DISCUSSION
Conductance Studies
1175, 853 cm–1.
In order to evaluate the influence of adding the
solutions of five different derivatives of xanthenes on
the molar conductance of Y3+ cation in pure AN and
MeOH, the conductivity of the solutions at a constant
salt concentration (1.00 × 10–4 mol L–1) was moni-
tored with increasing the concentration of the ligands
at various temperatures. A typical series of molar con-
ductance versus ligand/cation mole ratio plot for the
formation of (3,6,6-Tetramethyl-9-(4-chlorophenyl)-
1,8-dioxo-octahydroxanthene·Y3+) complex in pure
MeOHat different temperatures is shown in Fig. 1. As
it is seen from this figure, the molar conductivity grad-
ually increases after addition of the ligand to the solu-
1H NMR (DMSO-d6) δH 400 MHz 1.03 (s, 6H),
1.12 (s, 6H), 2.07 (dd, 4H), 2.40 (s, 4H), 2.43 (s, 3H),
4.69 (s, 1H), 6.80–7.28 (m, 4H) [24] (Scheme 5).
Apparatus
The conductance measurements were performed
using a digital Jenway conductometer, model 4510 at a
frequency of 1 kHz in a water bath thermostat
(LAUDA) with a precision of 0.1°C. The electrolytic
conductance was measured using a cell consists of two
platinum electrodes to which an alternating potential tion of Y3+cation. This behavior indicates that the
complexed form of the Y3+cation is more mobile than
the free solvated cation. In fact the complexation reac-
was applied. A conductometric cell with a cell con-
stant of 0.98 cm–1 was used throughout the studies.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 61
No. 2
2016

SOLVENT INFLUENCE UPON COMPLEX
253
Table 2. logKf values of the complexes formed between (phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-chlorophenyl, 4-
nitrophenyl) 9-substituted 1,8-dioxo-octahydroxanthene and Y3+ in AN and MeOH at different temperatures
logKf SDa
Medium/Ar
15°C
25°C
35°C
45°C
C6H5-
Pure AN
2.70 0.10
2.72 0.08
2.79 0.09
2.62 0.05
2.50 0.18
2.79 0.09
2.50 0.17
2.55 0.16
Pure MeOH
4-MeOC6H4
Pure AN
Pure MeOH
4-MeC6H4
Pure AN
Pure MeOH
4-ClC6H4-
Pure AN
2.82 0.07
3.67 0.06
2.68 0.16
2.55 0.15
2.50 0.15
2.85 0.08
2.76 0.10
2.71 0.13
b
2.50 0.23
2.53 0.17
2.53 0.18
2.70 0.13
2.51 0.20
2.53 0.17
2.61 0.10
b
b
b
2.69 0.26
b
Pure MeOH
4-NO2-C6H4
Pure AN
3.86 0.11
3.60 0.24
3.57 0.17
2.74 0.11
2.69 0.15
2.69 0.13
2.76 0.09
2.53 0.17
2.56 0.17
2.56 0.14
2.55 0.12
Pure MeOH
a
b
SD standard deviation. With high uncertainty.
tion is a competitive reaction between the ligand and ometry of the complexes formed between the organic
ligands and the metal cation is 1 : 1 [M : L].
the solvent molecules for the metal cation in solutions.
Upon complexation of the Y3+ cation with the studied
The corresponding molar conductance versus
ligands, the ligands molecules replace the solvation ([L]t/[M]t) plots do not illustrate a considerable
sheath around the metal ion and as a result, the sol- change in their slopes at a mol ratio of about 1, which
indicate that the 1 : 1 complexes formed between the
Y3+ cation and the studied ligands are relatively weak.
In order to make more clear the 1 : 1 [M : L] complex-
ation model, the fitting and experimental curves for
(3,6,6-Tetramethyl-9-(4-chlorophenyl)-1,8-dioxo-
octahydroxanthene·Y3+) complex (at 15°C in pure
MeOH) are shown in Fig. 2. As is evident in this fig-
ure, there is a very good agreement between the fitting
and experimental data, which indicates a 1 : 1 stoichi-
ometry for the complexes formed between the Y3+ cat-
ion and the organic synthesized ligands. The forma-
tion constants of the 1 : 1 complexes formed between
the five synthesized ligands and Y3+ cation at each
temperature were obtained from changes of the molar
conductivity as a function of the ligand to metal cation
molar ratios plots, using a non-linear least square
computer program, GENPLOT [25]. It should be
noted that, in the calculation of the stability constants of
the complexes, association into ion pairs was considered
to be negligible at the highly dilute experimental concen-
trations used. Since the ligand concentration in solutions
was also sufficiently low (<2.00 × 10–3 mol L–1), correc-
tions for viscosity changes were also neglected.
vated complexes become less bulky and more mobile
than the solvated cation, therefore, the molar conduc-
tance increases upon addition of the ligand to the cat-
ion solution. Similar behavior was observed in all of
the other studied systems. The conductometric data
show that in all studied solvent systems, the stoichi-
190
180
170
160
150
140
130
0
2
4
6
[L]t/[M]t
The values of formation constant (logKf) of the
Fig. 2. The fitting and experimental (filled diamond).
complexes formed between Y3+ cation and the studied
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 61 No. 2 2016

254
BASAFA et al.
ligands in pure AN and MeOH at different tempera-
tures are summarized in Table 2. As it clear from this
table, the order of stability of the complexes formed
between the organic ligands and Y3+cation in pure
MeOH at 45°C is: (3,6,6-Tetramethyl-9-(4-chloro-
phenyl)-1,8-dioxo-octahydroxanthene·Y3+) > (3,6,6-
Tetramethyl-9-(4-methoxyphenyl)-1,8-dioxo-octa-
hydroxanthene·Y3+) > (3,6,6-Tetramethyl-9-(4-phe-
7.5
6.5
6.0
5.5
5.0
4.5
6.32573
6.114399
5.87282
5.84322
nyl)-1,8-dioxo-octahydroxanthene·Y3+)
≈
(3,6,6-
Tetramethyl-9-(4-nitrophenyl)-1,8-dioxo-octahy-
droxanthene·Y3+) > (3,6,6-Tetramethyl-9-(4-methyl-
phenyl)-1,8-dioxo-octahydroxanthene·Y3+), but in
the case of pure AN at the same temperature the sta-
bility order changes to:
0.00310
0.00320
0.00330
0.00340
0.00350
0.00315
0.00325 0.003350 0.00345
1/T
Fig. 3. van’t Hoff plots for (3,6,6-Tetramethyl-9-(4-phenyl)-
1,8-dioxo-octahydroxanthene·Y ) complex in pure AN.
(3,6,6-Tetramethyl-9-(4-methoxyphenyl)-1,8-dioxo-
3+
octahydroxanthene·Y3+) > (3,6,6-Tetramethyl-9-(4-
nitrophenyl)-1,8-dioxo-octahydroxanthene·Y3+)
>
(3,6,6-Tetramethyl-9-(4-methylphenyl)-1,8-dioxo-
octahydroxanthene·Y3+) ≈ (3,6,6-Tetramethyl-9-(4-
phenyl)-1,8-dioxo-octahydroxanthene·Y3+) > (3,6,6-
Tetramethyl-9-(4-chlorophenyl)-1,8-dioxo-octahy-
droxanthene·Y3+). As is seen from Table 2, the stability
of the 1 : 1.
CP is equal to zero over the entire temperature range
investigated. The standard Gibbs energy change
°
(
) for the complexation process was calculated
ΔGc
from the following equation:
°
ΔGc,298.15 = −RTlnKf .
(1)
[M : L] complexes formed between the Y3+ cation
and the studied organic ligand containing different
electron donor (OMe, Me) and electron acceptor
(NO2, Cl) aryl substituent in pure AN system at 35°C
is the same. It seems that at this temperature, AN acts
as a leveling solvent and level effect of the electron
donor and electron acceptor aryl substituent in the
complexation process. Moreover, the experimental
results indicate that the stability order of the com-
plexes may change with the temperature. These
changes are probably due to the changes in the solva-
tion number of the cations, ligand and even the result-
ing complexes with the nature of the medium and also
temperature. These behavior sindicate the critical role
of solvent in local structure optimization and complex
stabilization in the host-guest recognition processes.
Thus, the complex stability is known to vary drastically
according to the nature of solvent in which the reac-
tion occurs [26].
°
The changes in standard entropy (
) were calcu-
ΔSc
lated from the Gibb’s–Helmholtz equation:
ꢀ
ꢀ
ꢀ
ΔGc,298.15 = ΔHc − 298.15ΔSc .
(2)
The calculated standard thermodynamic parame-
ters for the complexation reactions are summarized in
Table 3. As is evident from this table, the calculated
thermodynamic parameters for the complexation pro-
cess between Y3+ cation and the synthesized organic
ligands, show that in some cases, the changes in the
standard enthalpy for the complexation reactions
°
(
) are negligible, therefore, it seems that the com-
ΔHc
plexation processes in these non-aqueous solvents are
probably athermic, on the other hand, the values of
°
the standard entropy (
) in these systems are posi-
ΔSc
tive, therefore, the complexation reactions between
the studied ligands and the metal cation in these
organic solvents are entropy stabilized. But in some of
the complexation systems, the changes in the standard
enthalpy is negative, therefore, the complexation pro-
cesses in these systems are exothermic.
Thermodynamic Calculations
The thermodynamic quantities for complexations
reactions between the Y3+ cation and the studied
organic ligands were obtained from temperature
dependence of the stability constants of the resulting
1 : 1 [M : L] complexes using the van’t Hoff plots. The
van’t Hoff plots of lnKf versus 1/T for all of the inves-
tigated systems were constructed. For example, the
van’t Hoff plot for (3,6,6-Tetramethyl-9-(4-phenyl)-
1,8-dioxo-octahydroxanthene·Y3+) complex in AN is
shown in Fig. 3. The values of the standard enthalpy
CONCLUSIONS
The results obtained for the complexation reactions
between five different 9-aryl substituted 1,8-dioxo-
octahydroxanthenes as organic ligands and Y3+ metal
cation in methanol (MeOH) and acetonitrile (AN) at
different temperatures using the conductometric
°
(
) for the complexation reactions were calculated method, show that the stability and thermodynamics
ΔHc
by the slope of the van’t Hoff’s isochors as suming that of the complexation reactions are governed by the sol-
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 61
No. 2
2016

SOLVENT INFLUENCE UPON COMPLEX
255
Table 3. Thermodynamic parameters for complexes formed between (phenyl, 4-methoxyphenyl, 4-methylphenyl, 4-chlo-
rophenyl, 4-nitrophenyl) 9-substituted 1,8-dioxo-octahydroxanthene and Y3+ in AN and MeOH
SDa (25°C), kJ mol–1
°
SDa, kJ mol–1
SDa, J mol–1 K–1
Medium/Ar
°
°
ΔSc
ΔGc
ΔHc
C6H5-
b
Pure AN
–15.97 0.51
–14.96 0.32
–12.42 3.49
~0
Pure MeOH
4-MeOC6H4
Pure AN
Pure MeOH
4-MeC6H4
Pure AN
Pure MeOH
4-ClC6H4-
Pure AN
Pure MeOH
4-NO2-C6H4
Pure AN
50.18 1.07
–15.3 3 0.93
–14.54 0.88
~0
~0
52.09 3.12
48.77 2.95
b
b
–15.38 0.76
–15.78 0.52
–11.37 4.44
b
b
b
–15.38 1.49
–45.19 9.99
b
b
–14.25 1.32
–14.45 0.99
~0
~0
47.79 4.46
48.47 3.32
Pure MeOH
a
b
SD standard deviation. With high uncertainly.
vent medium. According to the conductometric data, values of entropy characterized the formation of some
complexes in solution.
in all cases, the stoichiometry of the resulting com-
plexes is 1 : 1 [ML]. The order of stability constant of
the complexes formed between the studied ligands and
Y3+ metal cation in pure MeOH at 45°C was found to
ACKNOWLEDGMENTS
The authors gratefully acknowledge the support of
this research by Islamic Azad University, Mashhad
Branch, Iran and Ferdowsi University of Mashhad,
Iran.
be:
(3,6,6-Tetramethyl-9-(4-chlorophenyl)-1,8-
dioxo-octahydroxanthene·Y3+) > (3,6,6-Tetramethyl-
9-(4-methoxyphenyl)-1,8-dioxo-octahydroxanthene ·
Y3+) > (3,6,6-Tetramethyl-9-(4-phenyl)-1,8-dioxo-
octahydroxanthene·Y3+) ≈ (3,6,6-Tetramethyl-9-(4-
nitrophenyl)-1,8-dioxo-octahydroxanthene·Y3+)
>
REFERENCES
(3,6,6-Tetramethyl-9-(4- Methylphenyl)-1,8-dioxo-
octahydroxanthene·Y3+), but in the case of AN at
45°C it changes to: (3,6,6-Tetramethyl-9-(4-methoxy-
phenyl)-1,8-dioxo-octahydroxanthene · Y3+) > (3,6,6-
Tetramethyl-9-(4-nitrophenyl)-1, 8-dioxo-octahy-
droxanthene·Y3+) > (3,6,6-Tetramethyl-9-(4-methyl-
phenyl)-1, 8-dioxo-octahydroxanthene·Y3+) ≈ (3,6,6-
Tetramethyl-9-(4-phenyl)-1,8-dioxo-octahydroxan-
thene·Y3+) > (3,6,6-Tetramethyl-9-(4-chlorophenyl)-
1,8-dioxo-octahydroxanthene·Y3+). The results obtained
in this investigation indicate that the order of selectiv-
ity of the synthesized organic ligands for the Y3+ metal
cation is changed by the nature of the non-aqueous
solvent and even with the temperature. The standard
thermodynamic parameters obtained for the complex-
ation reactions show that in some cases, the complex-
ation processes between the studied ligands and the
metal cation are athermic but in the other cases, the
complexation processes are exothermic and positive
1. J. P. Poupelin, G. Saint-Rut, O. Fussard-Blanpin,
et al., Eur. J. Med. Chem. 13, 381 (1978).
2. R. W. Lambert, J. A. Martin, K. E. Merrett, et al.,
Chem. Abstr. 126, 212377 (1997).
3. R. S. Varma, Tetrahedron 58, 1235 (2002).
4. R. M. Ion, Prog. Catal. 2 (1), 55 (1997).
5. T. Hideo, Chem. Abstr. 95, 80922b (1981).
6. K. Chibale, M. Visser, D. V. Schalkwyk, et al. Tetrahe-
dron 59, 2289 (2003).
7. R. M. Ion, D. Frackowiak, A. Plannerand, and K. Wik-
toromicz, Acta Biochim. Pol. 45, 833 (1998).
8. A. Banerjeeand and A. K. Mukherjee, Stain Technol.
56 (2), 83 (1981).
9. S. M. Menchen, S. C. Benson, J. Y. L. Lam, et al.
Taing, Chem. Abstr. 139, 54287f (2003).
10. R. J. Sarmaand and J. B. Baruah, Dyes Pigm. 64 (1), 91
(2005).
11. G. Malaise, L. Barloyand, J. A. Osborn, Tetrahedron
Lett. 42, 7414 (2001).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 61 No. 2 2016

256
BASAFA et al.
12. G. H. Rounaghi, G. N. Gerey, and M. S. Kazemi, 20. G. H. Rounaghi, M. Mohajeri, S. Ashrafi, et al., J. Incl.
J. Incl. Phenom. Macrocyclic. Chem. 55, 167 (2006).
Phenom. Macrocycl. Chem. 58, 1 (2007).
13. F. Razghandi, G. H. Rounaghi, and Z. Eshaghi, J. Incl.
21. G. H. Rounaghi and R. Sanavi, Pol. J. Chem. 80, 719
Phenom. Macrocyclic. Chem. 73, 87 (2012).
(2006).
14. A. Gherrou, H. J. Buschmannand, and E. Scholl-
22. M. Chamsaz, G. H. Rounaghi, and M. R. Sovizi, Russ.
meyer, Thermochim. Acta 425, 1 (2005).
J. Inorg. Chem. 50, 413 (2005).
15. A. Pankiewicz, G. Schroeder, B. Brzezinskiand, and
23. A. S. Waghmare, K. R. Kadam, and S. S. Pandit, Arch.
F. Bartl, J. Mol. Struct. 749, 128 (2005).
Appl. Sci. Res. 3, 423 (2011).
16. G. H. Rounaghiand and A. I. Popov, Polyhedron. 5,
24. H. N. Karade, M. Sathe, M. P. Kaushik, ARKIVOC.
1935 (1986).
XIII, 252 (2007).
17. M. H. Soorgi, G. H. Rounaghi, and M.S. Kazemi,
Russ. J. Gen. Chem. 78, 1866 (2008).
25. Genplot: A Data Analysis and Graphical Plotting Pro-
gram for Scientists and Engineers (Computer Graphic
Service, Ithaca, 1989).
18. Y. Kudo, J. Usami, S. Katsutaand, and Y. Takeda,
J. Mol. Liq. 123, 29 (2006).
19. A. Hosseinzadehattar, G. H. Rounaghi, and M. H. Arbab- 26. W. Lu, W. Qiu, J. Kim, et al., Chem. Phys. Lett. 394,
zavvar, J. Coord. Chem. 65, 3592 (2012). 415 (2004).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 61
No. 2
2016