87 Complexation Of P-Sulphonatocalix[4]Arene

Complexation Of P-Sulphonatocalix[4]Arene And Transition Metal In Optimized Temperature

K. Zare 1, 2, N. Shadmani 3,*, Z. Yousefian 4

1Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran

2Department of Chemistry, Shahid Beheshti University, Evin, Tehran, Iran

3Young Researchers and Elite Club, Rasht Branch, Islamic Azad University, Rasht, Iran

Email: n.shadmani@gmail.com , Fax: +981315551007

4 Department of Chemistry, Shahre -Rey Branch, Islamic Azad University, Tehran, Iran

Abstract

At the present study, the complexation ability of the 25, 26, 27, 28- tetrahydroxy -5, 11, 17, 23-

tetrasulphonic-calix[4]arene towards Tungsten (VI) was studied in aqueous solutions at temperature

298.15K using UV-Vis spectrophotometric method. A1:1 complex was formed between calixarene and

Tungsten (VI) ion. The ΔG˚, ΔH˚, and ΔS˚ of reaction obtained and they were negative, means reaction is

spontaneous, complex formation is exothermic and less disordering, respectively.

Keyword : Supramolecular chemistry; p-Sulphonatocalix[4]arene; Spectrophotometric method;

Thermodynamic parameter

Introduction

Calixarenes are a group of macro cyclic

compounds that contain phenolic units, which

connected together by methylene bridges to

form hydrophobic cavity [1-4]. They can be

prepared by the base-induced reaction of

certain p-substituted phenols with

formaldehyde. The structure of calixarene

characterized according to the methylene

rotation [5-8]. In recent years, the water-

soluble calix[n]arene derivatives have received

considerable attention because of their

selective metal ion binding properties in

aqueous solutions, the formation of basket- like

bilayer structures in the solid state, and the

observation of OH hydrogen bonding [9-14].

There are many advantages for using calixarene

as host molecules. Weak London forces,

hydrogen bonding, π-π interaction, and dipole-

dipole moments play important roles in

complex formation and drug release [15-18].

The studies about complex formation between

p-sulphonatocalix[4]arena (SC4) with main

elements, transition metals, anti-cancer and

anti-HIV drugs as well as with additional organic

supramolecular building components have been

reported [19]. Calixarenes have been studied in

the context of electrochemical selective sensor,

liquid crystals, mimic enzyme, uranium

extraction from sea [20-22], as stationary

phases and as adsorbent in solid phase

extraction [23]. P-sulphonatocalix[n]arene as a

water-soluble calixarene may selectively include

various guests according to its cavity size and

hydrophobicity in a manner similar to

cyclodextrins. Up to now, several Oxo and

Journal of Nano Chemical Agriculture , Vol(1) , No(3) 88

Chloro tungsten (VI) complexes with

calix[4]arene have been prepared. The new

structures of some W(VI) calixarene complexes

such as [W(tbcalix)(eg)], [WO(tbcalix)] and

[W(tbcalix)Cl2] (tbcalix = tetravalent anion of p-

tert-butyl calix[4]arene and eg= 1,2

ethanediolato dianion) were synthesized in

1998[24]. Complexes knewn to be suitable

starting material to the calixarene supported

organo tungsten complex [25-27]. In this work,

the previously synthesized of the 25, 26, 27, 28-

tetrahydroxy- 5, 11, 17, 23- tetrasulphonic

calix[4]arene (Fig.1) was used to form stable

complex with W(VI) ion in aqueous solutions

and complexation parameters were obtained

spectrophotometerically.

Material and Method

P-sulphonatocalix[4]arene was prepared

from the Louis Pasteur University, France,

(gratefully acknowledged), while Sodium

tungstate dehydrate (99.9%), NaOH and HCl

(titrazol 1N) were bought from Merck

(Darmstadt, Germany) with pure analytical

grades.

Absorption spectrum, in the wavelength range

of between 280 nm and 310 nm, measured on a

Scinco S-4100 (Korea) UV-Vis double beam

scanning spectrophotometer using 1cm quartz

cells. The temperature of system was controlled

at 298.15K by circulating water from an

isothermal bath. In all cases, the procedure

repeated at least three times and the average

of results used for calculations.

The titration of 2.5 ml solution of SC4 5×10-4

mol L-1was done with stepwise addition of the

tungsten (VI) solution, between 1.5× 10-2 to 3.5

× 10-2 mol L-1, both of the same pH 7.1. A

Jenway research pH-meter (model 827) used for

the pH measurements. The hydrogen ion

concentration measured with a Jenway

combination electrode. The UV-Vis spectrum

was of some combinations. These combinations

have small changes in between 280 nm to 310

nm. The data measured with the computer

using squad program. Fig. 2 shows the

absorbance of mixture in the between

wavelength of 280 nm and 310 nm. Complex

formation studied with metal to ligand

(0, 0.04, 0.08, 0.12, 0.16, 0.2, 0.24,

0.28, 0.32, 0.36, 0.4, and 0.44) by stepwise

titration of the certain concentration of SC4

with metal ion. The is representing the ratio

of metal to ligand (

). The absorbance has

decreased by increasing more amount of ion

metal to SC4, Fig. 2. The variation of UV

absorption spectrum of successive addition of

W (VI) solution to SC4 solution at 280 nm and

310 nm.

Results and Discussion

Assuming that the absorbance of the SC4

would change upon complexation with the W

(VI) metal ion, spectrophotometric

measurements carried out. The formation of

MpSC4q complex was characterized by changing

its stoichiometry, p and q, where M and SC4

represent metal ion and the ligand,

respectively. The stability constant of complex,

Kf, defined according to Eq.1.

[ ]

[ ] [ ]

The stability constant was determined using the

following method. Absorbance measured after

addition of metallic ion to the SC4 solution. The

absorption bands of the SC4 were decreased

after addition of metal ion solution in the range

89 Complexation Of P-Sulphonatocalix[4]Arene

of between 280 nm and 310 nm [28,29]. The

stoichiometric stability constants calculated

from the absorption data. The numbers of

experimental points were more than 30

(maximum 40) for each titration. In the

computer program, if we designate m

absorption spectra that will measured at n

wavelengths, the individual absorbance

readings thus can arranged in an m × n matrix R;

the m spectra form the R rows and the columns

consist of the n response carves gathered at the

different wavelengths. According to Beer’s low,

for a system with N absorbing components, R

can be decomposed into the product of a

concentration matrix c (m ×N) and a matrix of

the molar absorptivities S (N ×n). However,

because of the inherent noise in the measured

data, the decomposition does not represent R

exactly. The matrix T of the residuals was given

by the difference between CS and R, Eq.2.

In the fitting procedure, C and S matrices are

determined in which represent the original

matrix R best. The task of the fitting procedure

is to optimize the matrix (T) of the residuals, Eq.

2. According to the least squares criterion in

Eq.3, U is the sum of the squares of all elements

of T. It is the task of the non-linear least squares

fitting to find the set of parameters that result

in minimum of U [30].

∑∑

It was prevented for other proposed species

existed range of data. As expected poly nuclear,

the computer program systematically rejected

complexes. Taking into account a binuclear

complex alone or together with mononuclear

one does not improve the goodness of the fit

and even leads to the rejection of the model.

The model finally chosen, formed by MSC4,

resulted in a satisfactory numerical and

graphical fitting for all systems. The average

stability constant (log Kf), ΔH˚, ΔS˚, and ΔG˚ of

the 1:1 complex of SC4 with ion metal at

specified wavelengths and 298.15K was listed in

table 1. The standard enthalpy of reaction (ΔH°)

tells us how much heat will flow in or out of the

system. The standard Gibbs free energy (ΔG°)

tells us whether a reaction will take place. The

standard entropy of a reaction (ΔS°) tells us

whether the products or reactants are more

disordered. Standard Gibbs free energies at

298.15K calculated from Eq.4 and the results

shown in table 1. The negative value of ∆G°

shows a spontaneous forming complex. So, in

lower temperatures complex forms with, larger

value of stability constant and lower value of

standard Gibbs free energy. The results show

that the best complexation temperature is

298.15K. According to van’t Hoff Eq.4 and Eq.5,

∆Hº, ∆Sº, ∆G° can calculate respectively. Where

Kf is the solubility constant; H°, S°, G° are

the standard enthalpy, standard entropy,

standard free Gibss energy respectively; T is

absolute temperature; R is the universal gas

constant.

(

)

The curves of reaction between the SC4 and

Tungsten (VI) (Fig. 3) show a sharp break point

when the concentration ratio of metal ion to

SC4 forms a stable complex. The ΔG˚, ΔH˚, and

ΔS˚ of reaction obtained and they were

Journal of Nano Chemical Agriculture , Vol(1) , No(3) 90

negative, means reaction is spontaneous,

complex formation is exothermic and less

disordering, respectively. Its great equiblirium

constant (Kf) states high stability of complex Kf

=10 4.72 at 298.15K. According to the results

more stable complex was formed at low

temperatures.

Acknowledgements

Authors are grateful to University of Science

and Research Branch, Islamic Azad University,

Tehran, Iran. We are grateful to Shahid Beheshti

University, Tehran, Iran. We are grateful to

Young Researchers and Elite Club, Rasht Branch,

Islamic Azad University, Rasht, Iran for supports.

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Table 1. The average Log K and thermodynamic functions (SI unite) at 298.15K.

R2

Log K Temperature Complex

0.997 4.72±0.005

298.15 SC4-W(IV)

-178.356 H°/KJmol-1

-26.945

G°/KJmol-1

-0.508 S°/KJmol-1K-1

Fig. 1. The Structure of 25,26,27,28

tetra hydroxy- 5, 11, 17, 23

tetrasulphonic calix[4]arene.

93 Complexation Of P-Sulphonatocalix[4]Arene

Fig.2. The variation of UV absorption spectrum of successive addition of W (VI) solution to SC4 solution

at 280 to 310 nm.

Fig. 3. Spectrophotometric titration plots of the SC4 by metal ion at 298.15 K and 280 nm.

0

0.5

1

1.5

2

2.5

3

280 285 290 295 300 305 310

Abso

rban

ce

λ/nm

φ=metal ion φ=0 φ=0.04

φ=0.08 φ=0.12 φ=0.16

φ=0.2 φ=0.24 φ=0.28

φ=0.32 φ=0.36 φ=0.4

0.00

0.10

0.20

0.30

0.40

0.50

0.60

0.70

0.80

0.00 1.00 2.00 3.00

Aco

mp

lex

[M]/[SC4]