National Conference on Recent innovations in Applied Sciences and Humanities’ NCASH-2015 Volume : 4 | Issue : 10 | Special Issue Oct- 2015

2015 • ISSN No 2277 - 8179

Chemistry
Synthesis of Macrocyclic complexes and
KEYWORDS:
their Spectroscopic and ermal
investigation.

Nidhi Gupta University college of engineering, Punjabi university, Patiala, Punjab, India

ABSTRACT e lanthanide complexes derived from (3,5,13,15-tetramethyl 2,6,12,16,21-22- hexaazatricyclo[15.3.I1-17I7-

11]cosa-1(21),2,5,7,9,11(22),12,15,17,19-decane were synthesized. e complexes were found to have general
composition [Ln(L)X2·H2O]X, where Ln = La3+, Ce3+, Nd3+, Sm3+ and Eu3+ and X= NO3 − and Cl−. e ligand was characterized by elemental analyses,
IR and Mass spectral studies. All the complexes were characterized by elemental analyses, molar conductance measurements, magnetic
susceptibility measurements, IR, Mass, electronic spectral techniques and thermal studies. e ligand acts as a hexadentate and coordinates
through four nitrogen atoms of azomethine groups and two nitrogen of pyridine ring. e lanthanum complexes are diamagnetic while the
other Ln(III) complexes are paramagnetic. e spectral parameters i.e. nephelauxetic ratio (β), covalency factor (b1/2), Sinha parameter (δ%)
and covalency angular overlap parameter ( ) have been calculated from absorption spectra of Nd(III) and Sm(III) complexes. ese
parameters suggest the metal–ligand covalent bonding. In the present study, the complexes were found to have coordination number nine.

1. Introduction ethanol and dried under vacuum over P4O10 (Fig. 1).
e field of macrocyclic chemistry is developing very rapidly because
of its applications and importance in the area of coordination 2.3. Synthesis of complexes
chemistry [1]. e stability of macrocyclic metal complexes depends e lanthanide complexes of ligand (L) were prepared by the mixing
upon a number of factors, including the number and types of donor of hot ethanolic solution (20 mL) of corresponding metal salts (0.001
atoms present in the ligand and their relative positions with the mol), to a hot ethanolic solution (20 mL) of the ligand L (0.001 mol)
macrocyclic skeleton, as well as the number and size of the chelate with constant stirring on a magnetic stirrer. e reaction mixture
rings formed on complexation [2]. Macrocyclic complexes of was continuously stirred and refluxed on a water-bath for 30–35 h at
lanthanides are currently attracting much attention in the catalytic 75–80 ◦C. On cooling the reaction mixture at 0 ◦C for whole night,
cleavage of RNA [3], in radioimmunotherapy [4], toward tumor [5] product was precipitated out, washed with cold EtOH and dried
and DNA targeting [6], as contrast enhancing agents in magnetic under vacuum over silica gel.
resonance imaging [7], asNMRshift reagents [8], as
radiopharmaceuticals [9], as fluorescent robes in fluroimmunoassay
[10] and in laser technology [11]. ere is an emerging interest in the
application of macrocyclic ligands as effective metal ion chelators
and in the separation of lanthanides [12]. Coordination chemistry of
lanthanides has become of increasing significant in the last few years
due to the wide variety of applications [13] of lanthanides complexes
in supramolecular photochemistry [14] and in medicine [15].
Coordination compounds of the lanthanides are frequently used as
catalysts, which is demonstrated by the work of Shibasakiet al. [16],
Kobayashi and Ishitani [17] and others [18]. e design of
macrocycles capable of forming stable lanthanide (III) complexes
not only would allow further study of the coordination properties of
these metal ions but also would enable chemists to exploit more fully
certain important emerging properties of these complexes. e
preceding results provide a general guideline for the synthesis and
study of a series of lanthanide (III) complexes of macrocyclic ligands.
In this paper, we report the synthesis and characterization of
lanthanide metal complexes with a hexadentate ligand derived from
acetyl acetone and 2,6-diaminopyridine.

2. Experimental
2.1. Materials and methods
All the chemicals used were of AR grade and the solvents were dried
and distilled before use according to standard procedures.
Lanthanide salts and 2,6-diaminopyridne were purchased from Fig.1 Synthesis of ligands
Sigma Aldrich and used as received.
2.4. Analysis and physical measurements
2.2. Synthesis of macrocyclic ligand (L) Carbon, hydrogen and nitrogen analysis were carried out on a Carbo-
e ligand 3,5,13,15-tetramethyl-2,6,12,16,21,22-hexaazatricyclo Erba EA 1106 analyzer. Metal ion in the complexes were determined
[15.3.I1-17I7-11]cosa-1(21), 2,5,7,9,11(22),12,15,17,19-decaene[L] by volumetric method using EDTA solution [19].Molar conductivity
was prepared by dropwise addition of a hot ethanolic solution (20 was measured on an ELICO (CM 82T) conductivity bridge with a cell
mL) of acetyl acetone (2.0 g, 0.02 mol) to a hot ethanolic solution (20 having a cell constant of 0.51cm−1. e magnetic moment was
mL) of 2,6-diaminopyridine (2.1826 g, 0.02 mol) with constant determined at room temperature on a Gouy balance using
stirring in a 2:2 molar ratio. e solution was refluxed and stirred for 7 Hg[Co(SCN)4] as a callibrant. e electronic spectra of the complexes
h at 75 ◦C in the presence of few drops of conc. HCl. On cooling the were recorded on a ShimazduUVmini-1240 spectrophotometer
reaction mixture a dull white colored crystalline product was using DMSO as a solvent. IR spectra were recorded as CsI pellets on a
precipitated out. It was filtered, washed several times with cold FT-IR spectrum BX-II spectrometer in the region 200–4000cm−1.

Research Paper IJSR - INTERNATIONAL JOURNAL OF SCIENTIFIC RESEARCH 23

Volume : 4 | Issue : 10 | Special Issue Oct- 2015 • ISSN No 2277 - 8179 National Conference on Recent innovations in Applied Sciences and Humanities’ NCASH-2015
Electron impact mass spectrum was recorded on JEOL. JMS, DX-303 3.3. Mass spectrum of the ligand (L)
mass spectrometer. TG measurements of the complexes were carried e mass spectrum of the ligand (L) shows the peaks at m/z = 346
out in a nitrogen atmosphere on a Rigaku thermoflex instruments (50%) and 347. ese peaks correspond to the M+ (parental ion) and
using a limiting temperature of 600 ◦C and heating rate 10 ◦C/min. M+ +1, 13C isotope. e peak at m/z = 331, 316, 301 and 286 (70%) are
due to the stepwise removal of the four methyl groups from the
3. Result and discussion macrocyclic ligand. e intensity of the peak at 286 is 70% because it
3.1. Composition and coordination geometry corresponds to the macrocyclic moiety. A peak of very high intensity
e analytical data of complexes indicate that all the complexes have (100%) is also present at m/z=79 which is the base peak due to the
the general composition [Ln(L)X2·H2O] X, where Ln = La3+, Ce3+, Nd3+, pyridine ring. Some other peaks are also present in the spectrum at
Sm3+ and Eu3+ and X=NO3− and Cl−. All the complexes are sparingly 246, 169, 143, 103, 40, 26 and 15 due to the other fragmented ions [31].
soluble in common organic solvents such as ethanol and methanol e peaks area provides an idea of abundance of these ions.
but highly soluble in DMF and DMSO. Molar conductance values of
all the complexes in DMF fall in the expected range of 1:1 electrolytes
[20].

3.2. IR spectra
e IR absorption bands, which provide information about the
formation of macrocyclic ligand and the mode of coordination in its
complexes are given in Table 2. e spectrum displays a strong band
at 1687cm−1 [21] corresponding to (C- N) stretching vibration on
complex formation, the (C- N) band shows the negative shift [22]
which indicates that the nitrogen atom of azomethine group is
coordinated to metal ion [23,24]. e spectrum also shows the bands
at 1487cm −1 , 666cm −1 and 429cm −1 due to the pyridine ring
deformation, in-plane-ring-deformation and out-of plane-ring Fig. 3. Mass spectrum of ligand (L).
deformation, respectively. ese absorption bands show the positive
shift in complexes which indicates that the nitrogen of pyridine ring 3.4. Electronic spectra
is involved in coordination [25]. is mode of coordination of ligand e electronic spectra of the complexes were recorded in DMSO
is also supported by appearance of band corresponding to (M–N) in solution. Nd(III) and Sm(III) complexes display four electronic
the range 421–492cm−1 [26]. e appearance of various IR bands in spectral bands in the range 9112–11507cm−1, 11305–12468cm−1,
the nitrato complexes clearly reveals the presence of coordinated 13550–18540cm−1 and 17182–22331cm−1 [33–35], whereas in other
and uncoordinated NO3 ions. ese bands are found in the range complexes bands are appeared only in the ultra violet region. e
1410–1461cm−1, 1317–1355cm−1 and 1012–1077cm−1. e difference of assignments of these bands are given in Table 3. e complexes
NO stretching vibration is 93–106cm − 1 which suggests the exhibit effective enhancement in the intensity of “hypersensitive”
monodentate coordination [27] of nitrate groups. e appearance of bands from which nephelauxetic effect (β) is calculated by using the
strong bands in the range 1384–1390cm−1 indicate the presence of following expression:
ionic nitrate [28] . e chloro complexes show the bands
corresponding (Ln–Cl) [29] in the region 311–326cm−1 (Fig. 2).
β is the measure of the metal–ligand covalent bonding. e value of
is utilized to estimate the covalency factor (b1/2), Sinha parameter i.e.
degree of metal–ligand covalency (β) and the covalency angular
overlap parameter (η).

4. ermal studies

e thermogravimetry (TG) analyses of the complexes were carried

in the temperature range 30–60 C in a static nitrogen atmosphere.
All the complexes undergo first step decomposition with

weight loss exp. 2.52–2.99% (ca. 2.59–2.95%), between 165 and 225 ◦C
due to the loss of the one coordinated water molecule. In the second
step decomposition of the complexes show weight loss exp.
17.15–27.04% (ca. 17.09–26.99%) in the temperature range 315–375
◦C due to the removal of the coordinated and uncoordinated anions.
e third step decomposition is due to the loss of the ligand exp.
49.91–56.79% (ca. 49.85–56.72%) in the temperature range 450–540
◦C .e final residues was analyzed by IR spectra and identified as
metal oxide which is corresponding to the calculated value (Fig. 8).

Fig. 2. (a) IR spectrum of ligand (L). (b) IR spectrum of

[Nd(L)(NO3)2 H2O]NO3. (c) IR spectrum of [Ce(L)(NO3)2·H2O]NO3. Fig. 4. TGA curve of the complex [La(L)Cl2·H2O]Cl.

24 IJSR - INTERNATIONAL JOURNAL OF SCIENTIFIC RESEARCH Research Paper

National Conference on Recent innovations in Applied Sciences and Humanities’ NCASH-2015 Volume : 4 | Issue : 10 | Special Issue Oct- 2015 • ISSN No 2277 - 8179
5. Structure of the complexes
On the basis of above spectral studies the following structure may be
suggested for the complexes (Fig. 9).

Fig. 5. Structure of complexes with L. Where Ln = La3+, Ce3+,

Nd3+, Sm3+ and Eu3+ and X= Cl− and No3−.

6. Conclusion
In this paper, we describe the synthesis and characterization of a
hexadentate macrocyclic ligand and its La3+, Ce3+, Nd3+, Sm3+ and Eu3+
complexes. On the basis of absorption spectra we calculate the
different parameters i.e. nephelauxetic ratio (β), covalency factor
(b 1/2 ), Sinha parameter (δ%) and covalency angular overlap
parameter (η) for Nd(III) and Sm(III). e values of these parameters
suggest the metal–ligand covalent bonding. Except La(III), all the
complexes are paramagnetic in nature. e thermal studies reveal
the presence of coordinated water molecule. All the complexes were
found to have coordination number nine.

Acknowledgement
e authors are thankful to the NPL, New Delhi and Panjabi
university, Patiala in carrying out the research work.

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