J Incl Phenom Macrocycl Chem (2009) 64:49–56

DOI 10.1007/s10847-009-9535-8

ORIGINAL ARTICLE

Study of complex formation between 18-crown-6 and diaza-18-

crown-6 with uranyl cation (UO22+) in some binary mixed aqueous
and non-aqueous solvents
M. Ansari Fard Æ G. H. Rounaghi Æ M. Chamsaz Æ
K. Taheri

Received: 20 October 2008 / Accepted: 5 January 2009 / Published online: 23 January 2009
Ó Springer Science+Business Media B.V. 2009

Abstract The complexation reaction between UO22? (18C6
UO22?) complex in pure studied solvents was found
cation with macrocyclic ligand, 18-crown-6 (18C6), was to be: EtOH [ AN & NM [ PC & MeOH, but in the case
studied in acetonitrile–methanol (AN–MeOH), nitrometh- of (DA18C6
UO22?) complex it was : H2O [ MeOH [
ane–methanol (NM–MeOH) and propylencarbonate–ethanol EtOH.
(PC–EtOH) binary mixed systems at 25 °C. In addition, the
complexation process between UO22? cation with diaza-18- Keywords 18-Crown-6
Diaza-18-crown-6

crown-6 (DA18C6) was studied in acetonitrile–methanol UO22? cation
Binary mixed aqueous and
(AN–MeOH), acetonitrile–ethanol (AN–EtOH), acetonitrile– non-aqueous solvents
Conductometry
ethylacetate (AN–EtOAc), methanol–water (MeOH–H2O),
ethanol–water (EtOH–H2O), acetonitrile–water (AN–H2O),
dimethylformamide–methanol (DMF–MeOH), dimethyl-
formamide–ethanol (DMF–EtOH), and dimethylformamide– Introduction
ethylacetate (DMF–EtOAc) binary solutions at 25 °C using
the conductometric method. The conductance data show that The understanding of the metal–ion chemistry of macro-
the stoichiometry of the complexes formed between (18C6) cyclic ligands has important implications for a range of
and (DA18C6) with UO22? cation in most cases is 1:1 [M:L], chemical and biochemical areas. Macrocyclic compounds
but in some solvent 1:2 [M:L2] complex is formed in solu- are polydentate ligands containing their donor atoms
tions. The values of stability constants (log Kf) of attached to a cyclic backbone. The first report on the
(18C6
UO22?) and (DA18C6
UO22?) complexes which synthesis of macrocyclic compounds (crown ethers) was
were obtained from conductometric data, show that the published in 1967 by Pedersen [1]. These synthetic mac-
nature and also the composition of the solvent systems are rocyclic ligands have been shown to form stable selective
important factors that are effective on the stability and even complexes with suitable cations in solutions [2]. Most of
the stoichiometry of the complexes formed in solutions. In all the applications of these macrocyclic ligands, are based on
cases, a non-linear relationship is observed for the changes their complexing ability with different metal cations. Many
of stability constants (log Kf) of the (18C6
UO22?) and researches have been carried out on a wide range of
(DA18C6
UO22?) complexes versus the composition of applications of these macrocyclic compounds in different
the binary mixed solvents. The stability order of areas such as construction of ion-selective electrode [3–5],
separation of metal cations [6, 7], as stationary phase in
chromatography columns [8–10], designing of chemical
M. Ansari Fard
K. Taheri
Department of Chemistry, Faculty of Sciences, sensors [11], recognition of isomers [12] and chemical
The University of Sistan and Baluchestan, Zahedan, Iran analysis [13].
Studies of crown ethers complexation with metal cations
G. H. Rounaghi (&)
M. Chamsaz
in different solvent systems, show that the understanding of
Department of Chemistry, Faculty of Sciences, Ferdowsi
University of Mashhad, Mashhad, Iran the interaction between these macrocyclic ligands and the
e-mail: [email protected] metal cations in solutions requires the study of various

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50 J Incl Phenom Macrocycl Chem (2009) 64:49–56

parameters governing the complexation processes. The Experimental

thermodynamic studies of such complexation reactions
also result in a better understanding of high selectivity of Reagents and solvents
these ligands towards different metal cations. Many
investigators have studied the thermodynamics of solution 18C6 (MERCK) was recrystallized from acetonitrile
of macrocyclic polyether complexes during the past two (MERCK) and dried under vacuum for 72 h at room
decades [14–17]. While the complexation of crown com- temperature. Diaza-18-crown-6 (MERCK) and uranyl
pounds with metal cations have been studied in aqueous nitrate hexahydrate (RIEDEL) were used without further
solutions and in a wide variety of pure organic solvents [2], purification. The solvents: acetonitrile, dimethylformam-
but a little attention has been paid to complexation of these ide, methanol, ethanol, ethylacetate, nitromethane and
macrocyclic ligands with metal cations in mixed binary propylencarbonate, all from (MERCK), were used with the
solvents. The interaction between uranyl cation with sev- highest purity.
eral macrocyclic ligands has been studied [18–22].
Aza-crown ethers are suitable complexing agents for Apparatus
transition and heavy metal cations because when one or
two oxygen donors in crown ethers are replaced by nitro- The conductance measurements were performed using a
gen atoms, the stability constants of complexes of the digital, WTW conductivity apparatus model LF2000 in a
resulting aza-crown ethers with alkali and alkaline earth water bath thermostated with a constant temperature within
metal cations become smaller than those of the corre- ±0.03 °C. The electrolytic conductance was measured
sponding crown ethers. In constract, the complexation using a cell consisting of two platinum electrodes to which
abilities with transition metal cations and also heavy metal an alternating potential was applied. A conductometric cell
cations which belong to a class of soft acids, increase with a cell constant of 0.958 cm-1 was used throughout the
markedly to the same level as the corresponding acyclic studies.
amines [23].
In this research we studied the complexation of 18- Method
crown-6 (Scheme 1) with uranyl (UO22?) cation in
methanol (MeOH), ethanol, (EtOH), acetonitrile (AN), The experimental procedure to obtain the stability con-
nitromethane (NM), propylencarbonate (PC) and in their stants of (18C6
UO22?) and (DA18C6
UO22?)
binary mixtures. We also studied the complexation pro- complexes was as follows: a solution of metal salt
cess of diaza-18-crown-6 (Scheme 1) with uranyl (5 9 10-4 M) was placed in a titration cell and the con-
(UO22?) cation in water (H2O), methanol (MeOH), eth- ductance of the solution was measured, then a step-by-step
anol (EtOH), dimethylformamide (DMF), ethylacetate increase in the crown ether concentration was performed
(EtOAc), acetonitrile (AN) and in their binary mixture by rapid transfer from crown ether solutions prepared in the
solutions at 25 °C using the conductometric method. The same solvent (2 9 10-2 M) to the titration cell using a
goal of the present work was investigation of the effect microburette. The conductance of the solution in the cell
of the solvent properties and also the composition of the was measured after each addition at 25 °C.
binary mixed solvents on the stoichiometry and the order
of selectivity of 18C6 and DA18C6 for UO22? in various
solvent systems. Results

The changes of molar conductance (Km) versus the ligand

to metal cation, [L]t/[M]t, for complexation of 18C6 and
DA18C6 with UO22? cation in various binary mixed sol-
vents were studied at 25 °C. [L]t is the total concentration
O O of the ligand and [M]t is the total concentration of uranyl
O O HN O UO22? cation. Three typical series of molar conductance
values as a function of ligand–metal cation mole ratios in
H2O–MeOH, H2O–EtOH and AN–MeOH binary systems
O O O NH are shown in Figs. 1, 2 and 3, respectively. The stability
O O constants of (18C6
UO22?) and (DA18C6
UO22?)
complexes in various solvent systems at 25 °C was cal-
18-crown-6 Diaza-18-crown-6
culated from variation of molar conductance as a function
Scheme 1 Structure of the ligands of Ligand/Cation mole ratios using a GENPLOT computer

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J Incl Phenom Macrocycl Chem (2009) 64:49–56 51

mole% MeO 400

275
mole % AN

250 350
85%
75%
cm mol )

225 100%
-1

300 55%

cm mol )
35%

-1
2

200
250
15%
-1

2
Λ m ( ohm

175
200

-1
0%

Λ m ( ohm
150
150
125

100
100

50
75
0 1 2 3 4 5
[ L ] t/ [ M ] t 0
0 1 2 3 4 5 6
Fig. 1 Molar conductance–mole ratio plots for (DA18C6
UO22?) [ L ] t/ [ M ] t
complex in H2O–MeOH binary systems at 25 °C
Fig. 3 Molar conductance–mole ratio plots for (DA18C6
UO22?)
complex in AN–MeOH binary systems at 25 °C
300

mole% EtOH
275 constants of (DA18C6
UO22?) and (18C6
UO22?)
complexes in various solvent systems are listed in Tables 1
250 and 2, respectively. The changes of stability constant
(log Kf) of (18C6
UO22?) complex with the composition
225
of the PC–EtOH, AN–MeOH and NM–MeOH binary
cm mol )
-1

200 0% systems, as well as, the changes of stability constant

(log Kf) of (DA18C6
UO22?) complex with the compo-
2

175 sition of the AN–MeOH, H2O–AN, H2O–MeOH and H2O–

EtOH binary solutions at 25 °C are shown in Figs. 4, 5, 6
-1
Λ m (ohm

150 and 7, respectively.

125 7% Discussion
100
As is evident from Figs. 1 and 2, addition of DA18C6 to
15%
75 55%
uranyl cations in H2O–MeOH and H2O–EtOH binary sol-
30% vent systems at 25 °C results in a decrease in molar
50 conductivity which indicates that the (DA18C6
UO22?)
complex is less mobile than free solvated cation in these
25 binary solvent systems. Similar behavior was observed for
0 1 2 3 4 5 6
(DA18C6
UO22?) complex in DMF–MeOH and in H2O–
[ L] t/ [ M ] t
AN binary solvent systems. But as seen in Fig. 3, addition
Fig. 2 Molar conductance–mole ratio plots for (DA18C6
UO22?) of DA18C6 to uranyl cation in AN–MeOH binary solutions
complex in H2O–EtOH binary systems at 25 °C at 25 °C results in an increase in molar conductivity which
indicates that the (DA18C6
UO22?) complex in this sol-
program [24]. The details of the calculation of the stability vent system is more mobile than free solvated cation.
constants of complexes by conductometric method has Similar behavior was observed for (DA18C6
UO22?)
been described in reference [25]. The values of stability complex in AN–EtOH, DMF–EtOAc and AN–EtOAc

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52 J Incl Phenom Macrocycl Chem (2009) 64:49–56

Table 1 Log Kf values of (DA18C6
UO22?) complex in different binary mixed solvents at 25 °C
Medium Log Kf ± SDa Medium Log Kf ± SDa Medium Log Kf ± SDa

AN–MeOH H2O–MeOH DMF–MeOH

Pure AN c Pure H2O 4.26 ± 0.15 Pure DMF c
85% AN–15% MeOHb c 90% H2O–10% MeOHb 3.75 ± 0.09 85% DMF–15% MeOHb [6
75% AN–25% MeOH c 75% H2O–25% MeOH 3.89 ± 0.12 65% DMF–35% MeOH [6
55% AN–45% MeOH 4.58 ± 0.11 60% H2O–40% MeOH 3.84 ± 0.13 45% DMF–55% MeOH [6
35% AN–65% MeOH 4.85 ± 0.16 35% H2O–65% MeOH c 25% DMF–75% MeOH [6
15% AN–85% MeOH 3.92 ± 0.10 25% H2O–75% MeOH c 10% DMF–90% MeOH [6
Pure MeOH 2.72 ± 0.05 10% H2O–90% MeOH c Pure MeOH 2.72 ± 0.05
Pure MeOH 2.72 ± 0.05
AN–EtOH H2O–EtOH DMF–EtOH
Pure AN c Pure H2O 4.26 ± 0.15 Pure DMF c
80% AN–20% EtOH c 93% H2O–7% EtOH 4.28 ± 0.07 80% DMF–20% EtOH [6
60% AN–40% EtOH c 85% H2O–15% EtOH 3.97 ± 0.09 60% DMF–40% EtOH [6
40% AN–60% EtOH c 70% H2O–30% EtOH 3.67 ± 0.11 40% DMF–60% EtOH [6
20% AN–80% EtOH c 45% H2O–55% EtOH 4.76 ± 0.38 20% DMF–80% EtOH [6
Pure EtOH 2.48 ± 0.13 30% H2O–70% EtOH c Pure EtOH 2.48 ± 0.13
15% H2O–85% EtOH c
7% H2O–93% EtOH c
Pure EtOH 2.48 ± 0.13
H2O–AN AN–EtOAc DMF–EtOAc
Pure H2O 4.26 ± 0.15 Pure AN c Pure DMF c
90% H2O–10% AN 3.82 ± 0.10 90% AN–10% EtOAc c 80% DMF–20% EtOAc 2.46 ± 0.13
80% H2O–20% AN 3.75 ± 0.16 75% AN–25% EtOAc c 60% DMF–40% EtOAc 3.11 ± 0.03
65% H2O–35% AN c 55% AN–45% EtOAc c 40% DMF–60% EtOAc 4.24 ± 0.04
40% H2O–60% AN c 35% AN–65% EtOAc c 20% DMF–80% EtOAc 4.86 ± 0.10
20% H2O–80% AN 4.31 ± 0.16 15% AN–85% EtOAc c
Pure AN c
a
SD = Standard deviation
b
The composition of binary solvents is expressed in mole% of each solvent
c
Data can not be fitted in equation

Table 2 Log Kf values of (18C6
UO22?) complex in different binary mixed solvents at 25 °C
Medium Log Kf ± SDa Medium Log Kf ± SDa Medium Log Kf ± SDa

AN–MeOH NM–MeOH PC–EtOH

Pure AN 2.09 ± 0.26 Pure NM 2.09 ± 0.07 Pure PC 1.69 ± 0.12
75% AN–25% MeOHb 2.26 ± 0.11 85% NM–15% MeOHb 2.29 ± 0.06 75% PC–25% EtOHb 2.17 ± 0.14
55% AN–45% MeOH 3.08 ± 0.05 75% NM–25% MeOH 1.51 ± 0.08 50% PC–50% EtOH 1.57 ± 0.15
35% AN–65% MeOH 3.03 ± 0.11 55% NM–45% MeOH 1.92 ± 0.14 30% PC–70% EtOH 1.81 ± 0.24
15% AN–85% MeOH 1.88 ± 0.16 35% NM–65% MeOH 1.45 ± 0.14 15% PC–85% EtOH 1.76 ± 0.33
Pure MeOH 1.69 ± 0.33 15% NM–85% MeOH 1.68 ± 0.12 Pure EtOH 3.12 ± 0.04
Pure MeOH 1.69 ± 0.33
a
SD = Standard deviation
b
The composition of binary solvents is expressed in mole% of each solvent

binary mixed solvents, as well as, for (18C6
UO22?) solvation sphere. It seems that the UO22? cation is weakly
complex in AN–MeOH, NM–MeOH and PC–EtOH binary solvated in H2O–MeOH and H2O–EtOH solvent systems.
solutions. These behaviors can be explained on the basis of When this cation is complexed with crown ether, it

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J Incl Phenom Macrocycl Chem (2009) 64:49–56 53

3.4 5.5
AN - MeOH
5

4.5
3

Log kf
4

3.5
2.6
3
Log K f

2.5
0.4 0.6 0.8 1
2.2
mole fraction of MeOH

4.4 H 2O - AN
1.8
4.2

Log kf
4
1.4
0 0.2 0.4 0.6 0.8 1
3.8
mole fraction of EtOH

Fig. 4 Changes of stability constant (log Kf) of (18C6
UO22?) 3.6

complex with the composition of PC–EtOH binary system at 25 °C 0 0.2 0.4 0.6 0.8 1
mole fraction of AN
3.5
Fig. 6 Changes of stability constant (log Kf) of (DA18C6
UO22?)
AN - MeOH complex with the composition of AN–MeOH and H2O–AN binary
3 systems at 25 °C
Log K f

2.5

2
4.5
1.5 H2 O - MeOH
0 0.2 0.4 0.6 0.8 1 4
mole fraction of MeOH
Log Kf

2.4 3.5
2.2
NM-MeOH
Log K f

2 3
1.8
1.6 2.5
0 0.2 0.4 0.6 0.8 1
1.4 mole fraction of MeOH
1.2 5
0 0.2 0.4 0.6 0.8 1 H 2 O - EtOH
4.5
mole fraction of MeOH
4
UO22?)
Log Kf

Fig. 5 Changes of stability constant (log Kf) of (18C6
3.5

complex with the composition of AN–MeOH and NM–MeOH binary
systems at 25 °C 3
2.5
2
becomes bulkier which results in a decrease in the molar 0 0.2 0.4 0.6 0.8 1
conductivity of the solutions. On the other hand, it seems mole fraction of EtOH
that the UO22? cation is highly solvated in AN–MeOH Fig. 7 Changes of stability constant (log Kf) of (DA18C6
UO22?)
binary solutions. However, upon complexation of UO22? complex with the composition of H2O–MeOH and H2O–EtOH binary
cation with DA18C6, the ligand molecule replaces the systems at 25 °C

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54 J Incl Phenom Macrocycl Chem (2009) 64:49–56

solvation sheath around the cation and the moving entity noticeable that the order of decreasing the stabilities of
becomes less bulky and more mobile and, therefore, the (DA18C6
UO22?) and (18C6
UO22?) complexes are
molar conductivity increases. not consistent with the order of donor ability of these pure
As is shown in Figs. 1 and 2, in all cases, the slope of organic solvents as expressed by the Gutmann donor
corresponding molar conductivity versus Ligand/Cation number [30] (see Table 3). Similar results have been
mole ratio plots changes at the point where the ligand to observed for (DA15C5
UO22?) complex in PC, H2O,
cation mole ratio is about one which is an evidence for DMF and MeOH solvents [28]. Although the solvating
formation of a relatively stable 1:1 [M:L] complex between ability of a solvent as expressed by the Gutmann donor
DA18C6 and UO22? cation in these solutions. Similar number, plays a fundamental role in complexation reac-
behavior was observed for complexation of UO22? cation tions between metal cations and macrocyclic ligands, and a
with 18C6 in solutions. The spectroscopic study of uranyl solvent with a high donor number can compet strongly with
crown ether complexes in non-aqueous solvents, has shown the ligand for the cation, but the results obtained in this
that the crown ethers with six oxygen atoms form inclusion investigation indicate that the donor ability of a solvent
complexes with uranyl ion in the center cavity, but aza and, therefore, the cation solvation is not always a domi-
crowns coordinate externally to the uranyl ion [26]. In the nant factor in complexation processes and we should
case of 18-crown-6 a complex with a high coordination consider the solvation of the ligand, the resulting complex
symmetry is formed. The crystal structures of UO22? and even the solvation of counter ion in solutions.
complexes with DA18C6 have been studied and inclusion The complexation reaction between a metal cation with
complexes are reported in which the linear uranyl moiety is a ligand in solution which is an exchange process can be
included in to the macrocycle with hexagonal–bipyramidal written as:
coordination geometry [27].
ðmetalnþ ÞSx þ ðligandÞSy ¼ ðmetalligandÞnþ Sz
As is obvious from Fig. 3, in three AN–MeOH binary
systems (mole% AN = 15, 35 and 55%), the slope of the þ ðx þ y  zÞS
corresponding molar conductivity versus Ligand/Cation in which S is the solvent molecule, x, y and z are the
mole ratio plots changes at the point where the ligand to solvation numbers of metal cation, ligand and the resulting
cation mole ratio is about one which is an evidence for complex, respectively. Therefore, the change of free energy
formation of a 1:1 [M:L] complex between DA18C6 and of the solution, depends on the difference in affinity of
UO22? cation in these solutions, but it is interesting to note ligand and solvent for the metal cation and also the dif-
that in other compositions of this binary mixed solvent ference in affinity of the metal cation and solvent
(mole% AN = 75, 85 and 100%), the slope of each curve molecules for the ligand. In addition, the solvation of the
changes at the point where [L]t/[M]t is about two which is resulting complex is effective in the free energy of com-
an evidence for formation of a 1:2 [M:L2] complex plexation process. Therefore, in addition to solvation of the
between DA18C6 and UO22? cation in these solutions. metal cation, the solvation of the ligand and the resulting
These results reveal that the stoichiometry of the complex complex contribute to the overall free energy of complex
formed between DA18C6 and UO22? cation changes with formation in solutions [31].
the composition of AN–MeOH binary solutions. Similar The changes of stability constant (log Kf) of
results have been obtained for complexation of uranyl (18C6
UO22?) complex versus the solvent composition,
cation with diaza-15-crown-5 in AN–MeOH binary solvent in PC–EtOH, AN–MeOH and NM–MeOH binary mixed
systems [28], and also for complexation of Pb2? cation solvents are shown in Figs. 4 and 5 and the changes of
with aza-18-crown-6 in DMSO–H2O binary solutions [29].
The results obtained in this investigation indicate that the
property and also the composition of the solvent system are
Table 3 Donor number values for some of solvents
affective factors on stoichiometry and stability of the
complexes formed between DA18C6 and UO22? cation in Solvent Donor number (DN)
solutions. Nitrometane 2.7
As is evident from Table 1, the stability order of Acetonitrile 14.1
(DA18C6
UO22?) complex in pure studied solvents is: Propylencarbonate 15.1
H2O [ MeOH [ EtOH. Since the DA18C6 is probably Etylacetate 17.1
strongly solvated in MeOH and EtOH solutions, therefore, Ethanol 19.1
the complex is more stable in water compared to these
Methanol 20.0
alcoholic solutions. The data in Table 2, show that the
Dimetylformamide 26.6
stability order of (18C6
UO22?) complex in pure organic
Water 33.0
solvents is: EtOH [ AN & NM [ PC & MeOH. It is

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J Incl Phenom Macrocycl Chem (2009) 64:49–56 55

stability constant (log Kf) of (DA18C6
UO22?) complex References

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