J. Serb. Chem. Soc.

77 (11) 15891597 (2012)

JSCS4373

UDC 66.094.941+542.9+547.571+
547.551:541.8:542.913:535.371
Original scientific paper

Solvent-dependent synthesis and mono-hydrolysis of the

di-Schiff base of ()trans-1,2-cyclohexanediamine and
2-pyridinecarboxaldehyde in Cu(II), Co(II)
and Zn(II) complexes
MARYAM LASHANIZADEGAN* and MARZIEH SARKHEIL
Department of Chemistry, Faculty of Sciences, Alzahra University,
P. O. Box 1993893973, Tehran, Iran
(Received 3 December 2011, revised 24 March 2012)
Abstract: The Schiff base ligand trans-N,N-bis(2-pyridinylmethylene)-1,2-cyclohexanediamine (L) was synthesized. This ligand when stirred with 1 equivalent of MCl2xH2O (M = Cu, Co or Zn) in ethanol, undergoes partial hydrolysis of the imino bond and the resultant tridentate ligand (L) immediately
forms complexes with an N3 coordination sphere. The reactions of L with
MCl2xH2O (M = Cu, Co or Zn) in THF gave the complexes [ML]Cl2. The ligand (L) and the complexes [M(L)Cl]Cl and [ML]Cl2 were characterized by
elemental analysis, UVVis, FT-IR, 1H-NMR spectroscopy, GC/MS and their
luminescence properties. The 1H-NMR spectra of the ligand and its diamagnetic complexes were recorded in CDCl3 and DMSO solvents, respectively.
The obtained data confirmed that the donor N atoms in the ligand coordinated
to the metal ions. The luminescence studies show ligands and their complexes
display intraligand (*) fluorescence in MeOH solution and the solid state at
room temperature.
Keywords: mono-hydrolysis; Schiff base; solvent effect; fluorescence.
INTRODUCTION

Schiff base ligands have been in the chemistry catalogues for decades and
have played a key role as chelating ligands in main group and transition metal coordination chemistry. This is due to their ease of synthesis and stability under a
variety of oxidative and reductive conditions.15 Not only have they played an
influential role in the development of modern co-ordination chemistry,6 but they
can also be found at key points in the development of inorganic biochemistry,7
catalysis,8,9 medical imaging,10 optical materials11 and thin films.12,13 The formation of a Schiff base by condensation of diamine and carbonyl compounds is
* Corresponding author. E-mail: m_lashani@[Link]
doi: 10.2298/JSC111203035L

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well known.1417 The reverse process, i.e., the hydrolysis of Schiff bases in the
presence of a metal ion was observed by Ghosh and coworkers.18 It was observed that the hydrolysis is dependent on several factors, such as the pH of the
reaction medium,19 the size of the chelate rings formed by the diamine fragment
of the Schiff base,20,21 the coordinating ability of the counter anions,22,23 the
nature of the metal ions,20,21 the effect of carbonyl compounds,24 etc. In order to
investigate this type of reaction, the Schiff base trans-N,N-bis(2-pyridinylmethylene)-1,2-cyclohexanediamine was synthesized by condensation of ()trans1,2-cyclohexanediamine with 2-pyridinecarboxaldehyde in a 1:2 mole ratio, respectively. The reaction of this ligand with a metal chloride in ethanol resulted in
the hydrolysis of one of the imine bonds. On the other hand, reaction of this
ligand with a metal chloride in THF solvent resulted in the coordination of two
imino bonds to the metal. The details of the synthesis, structure, mass spectrum
and luminescence behaviours are described herein.
EXPERIMENTAL
Materials
All starting materials and solvents except ()trans-1,2-cyclohexanediamine (Alfa Aesar),
were purchased from Merck and were used without further purification. The synthetic reactions and work-up were realized in open air.
Physical measurements
The IR spectra (KBr discs, 5004000 cm-1) were recorded using a Bruker FTIR model
Tensor 27 spectrometer. The elemental analysis was performed in a 2400 Series II CHN analyzer, Perkin-Elmer, USA. The UVVis absorption spectra and fluorescence measurements
were recorded on a Perkin-Elmer Lambda 35 spectrophotometer and a Varian Cary Eclipse
1.1 spectrofluorometer, respectively. The 1H-NMR spectra were recorded on a Bruker 500
MHz model DRX spectrometer in CDCl3 and DMSO-d6 with TMS as the internal reference.
The mass spectrum of the ligand (L) was studied with a GC/MS Quadrupole Agilent 5973
MSD spectrometer.
Preparation of ligand (L)
A diethyl ether solution (5 ml) of 2-pyridinecarboxaldehyde (0.214 g, 2.00 mmol) was
added to diethyl ether solution (5 ml) of ()trans-1,2-cyclohexanediamine (0.114 g, 1.00
mmol). The mixture was stirred for 10 min and then kept in air to allow the solvent to
evaporate, whereby yellowish crystals of the ligand L were obtained in 90% yield.
Preparation of [M(L)Cl]Cl (13)
[Cu(L)Cl]Cl (1) was prepared by adding an ethanolic solution (10 ml) of CuCl22H2O
(0.170 g, 1.00 mmol) to an ethanolic solution (10 ml) of L (0.292 g, 1.00 mmol). The resulting
mixture was stirred around 1 h. Finally, the precipitate of complex 1 was recovered by
filtration, and washed several times with absolute ethanol and dried under vacuum at 65 C for
1 h. Yield: 44 %.
[Co(L)Cl]Cl (2) was prepared in a similar manner to 1 but using CoCl26H2O (0.237 g,
1.00 mmol). Yield: 31 %.
[Zn(L)Cl]Cl (3) was prepared in a similar manner to 1 but using ZnCl2 (0.136 g, 1.00
mmol). Yield: 60 %.

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Preparation of [ML]Cl2 (46)

[CuL]Cl2 (4) was prepared by adding a THF solution (20 ml) of L (0.292 g, 1 mmol) to a
THF solution (10 ml) of CuCl22H2O (0.170 g, 1.00 mmol). After stirring the resulting mixture for around 1 h, the precipitated complex was recovered by filtration, washed with THF
and Et2O and finally dried under vacuum at 65 C for 1 h. Yield: 41 %.
[CoL]Cl2 (5) was prepared in a similar manner to 4 but using CoCl26H2O (0.237 g, 1.00
mmol). Yield: 78 %.
[ZnL]Cl2 (6) was prepared in a similar manner to 4 but using ZnCl2 (0.136 g, 1.00
mmol). Yield 53 %.
RESULTS AND DISCUSSION

Synthesis and formulation

The ligand L (Scheme 1) was synthesized by condensation of a 1:2 mole
ratio of ()trans-1,2-cyclohexanediamine with 2-pyridinecarboxaldehyde. When
L reacts with MCl2H2O (M = Cu, Co or Zn) in ethanol, it undergoes partial
hydrolytic cleavage to form an N3 coordination sphere of copper(II) (1), cobalt(II) (2) and zinc(II) (3) complexes. When L reacts with MCl2H2O in THF,
[ML]Cl2 (M = Cu (4), Co (5) or Zn (6)) complexes with N4 coordination sphere
are formed.

Scheme 1. Synthetic routes to the ligand (L) and complexes 16.

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Some analytic and spectral data of the ligand and complexes 16

Ligand (L). Yield: 90 %; m.p.: 126 C; IR (KBr, cm1): 2931, 2853 (CH2/CH
stretching of cyclohexane ring), 1643 (C=N stretching of azomethine group) ,
772 (out-of-plane CH deformation); 1H-NMR (500 MHz, CDCl3, / ppm):
1.511.91 (8H, m, CH2), 3.553.57 (2H, m, CH), 7.227.91 (8H, m, aromatic),
8.558.57 (2H, d, J = 7.1 Hz ,CH=N); MS (m/z, (relative abundance, %)): 292
(M+, 100); UVVis (MeOH) (max / nm ( / L mol1 cm1)): 203 (16595), 236
(20417), 274 (11481).
[Cu(L)Cl]Cl (1). Yield: 44 %; m.p.: 230 C; IR (KBr, cm1): 3267, 3217
(NH stretching of primary amine), 2862, 2929 (CH2/CH stretching of cyclohexane ring), 1655 (C=N stretching of azomethine group), 776 (out-of-plane CH
deformation); UVVis (MeOH) (max / nm ( / L mol1 cm1)): 203 (12589), 235
(sh), 293 (6456), 304 (sh), 693 (b).
[Co(L)Cl]Cl (2). Yield: 31 %; m.p.: 190 C; IR (KBr, cm1): 3289, 3240
(NH stretching of primary amine), 2862, 2929 (CH2/CH stretching of cyclohexane ring), 1634 (C=N stretching of azomethine group), 777 (out-of-plane CH
deformation); UVVis (MeOH) (max / nm ( / L mol1 cm1)): 206 (24547), 283
(sh), 451 (sh), 537 (sh).
[Zn(L)Cl]Cl (3). Yield: 60 %; m.p.: 270 C; Anal. Calcd. for: C12H17N3ZnCl2:
C, 42.44; H, 5.05; N, 12.37 %. Found: C, 42.54; H, 5.06; N, 12.24 %; IR (KBr,
cm1): 3293, 3248 (NH stretching of primary amine), 2929, 2859 (CH2/CH
stretching of cyclohexane ring), 1663 (C=N stretching of azomethine group), 776
(out-of-plane CH deformation); 1H-NMR (500 MHz, DMSO-d6, / ppm):
1.051.96 (8H, m, CH2), 3.323.62 (2H, m, CH), 7.488.83 (5H, m, aromatic,
HC=N); UVVis (MeOH) (max / nm ( / L mol1 cm1)): 204 (13803), 240 (7413),
283 (7585), 392 (sh).
[CuL]Cl2 (4). Yield: 41 %; m.p.: 220 C; IR (KBr, cm1): 2926, 2867 (CH2/CH
stretching of cyclohexane ring), 1653 (C=N stretching of azomethine group), 782
(out-of-plane CH deformation); UVVis (MeOH) (max / nm ( / L mol1 cm1)):
208 (17782), 234 (sh), 290 (9332), 469 (323), 683 (b).
[CoL]Cl2 (5). Yield: 78 %; m.p.: 330 C; IR (KBr, cm1): 2931, 2868 (CH2/CH
stretching of cyclohexane ring), 1635 (C=N stretching of azomethine group), 775
(out-of-plane CH deformation); UVVis (MeOH) (max / nm ( / L mol1
cm1)): 205 (22908), 264 (sh), 566 (457).
[ZnL]Cl2 (6). Yield: 53 %; m.p.: 290 C; IR (KBr, cm1): 2932, 2862 (CH2/
/CH stretching of cyclohexane ring), 1639 (C=N stretching of azomethine group),
768 (out-of-plane CH deformation); 1H-NMR (500 MHz, DMSO-d6, / ppm):
1.421.89 (8H, m, CH2), 3.323.69 (2H, m, CH), 7.568.66 (10H, m, aromatic,
HC=N); UVVis (MeOH) (max / nm ( / L mol1 cm1)): 249 (7079), 258 (sh).

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IR and UVVis spectra of the ligand and complexes

In the IR spectrum of ligand L, a strong and sharp band due to the azomethine (C=N) appears at 1643 cm1. The bands at 2853 and 2931 cm1 are indicative of the presence of 1,2-cyclohexanediamine.
In the IR spectra of 13, the two primary NH2 stretching modes are seen at
around 32673293 and 32173248 cm1 as sharp bands (doublet) for the asymmetric and symmetric vibrations, respectively (Fig. 1). A strong absorption band
at 29292862 cm1 corroborates the presence of the 1,2-cyclohexanediamine
group in the complexes.25 The band due to azomethine (C=N) appears at 1655,
1634 and 1663 cm1 for complexes 13, respectively. In the IR spectra of complexes 46, the strong absorption bands at 29322857 cm1 corroborate the presence of the 1,2-cyclohexanediamine group in the complexes. The band due to
azomethine (C=N) appears at 1653, 1635 and 1639 cm1, respectively. A comparison of the IR spectra of 13 with 46 provides clear evidence of the hydrolytic cleavage that had occurred in one imine bond of L. The IR spectra of
complexes 46 exhibit bands typical of 2-substituted pyridines.26 These pyridine
bands are the four rings stretching vibrations (16041445 cm1), the ring breathing vibration at around 10261024 cm1 and the out-of-plane CH deformation

Fig. 1. IR spectra of ligand (L) and complexes 13.

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at around 782768 cm1. These compounds also show a strong band at around
16531635 cm1, assigned27 to the azomethine stretching vibration, which confirms the Schiff base nature of the coordinated L molecule.
The electronic spectra of complex 1 consist of one broad dd transition band
at 693 nm, as is usual for four coordinated Cu(II).28,29 The higher energy bands
are due to * or n* transition. Complex 2 shows one band at 531 nm and the
other at 451 nm indicating four coordinated geometry of the Co(II) complexes.30
The electronic absorption spectra of 4 and 5 show absorption band at 683 and
566 nm, respectively. The bands are typical of dd transition in a four coordinated environment around Cu(II) and Co(II).31 The electronic absorption spectra
of 3 and 6 show absorption bands at 204, 240, 283 and 392 nm and 249 and 258
nm, respectively. The bands are typical of intraligand transition.
1H-NMR

spectra of the ligand and complexes 3 and 6

The 1H-NMR spectra of the ligand (L) and complexes 3 and 6 were recorded
using CDCl3 and DMSO-d6 as solvent, respectively. Hydrogen atoms of the azomethine groups of L appeared at 8.558.57 ppm as a doublet. The aromatic
protons are found in the range 7.227.91 ppm as a multiplet. The hydrogen
atoms of the CH2/CH groups in the cyclohexane ring are observed in the 1.51
3.57 ppm range.12 In 3 and 6, a slight downfield shift of 0.20.3 ppm in the
resonance peaks corresponding to the aromatic and the azomethine protons is
noticeable. This fact confirms that the nitrogen atoms were coordinated to the
Zn(II) ion.3234
Luminescence studies
The photophysical data for the ligand and complexes 16 are listed in Table
I. The luminescence studies showed that complexes 13 exhibited an emission
band at 413, 426 and 411 nm, respectively, in methanol solution and in the solid
an emission band at 397, 385 and 387 nm, respectively, which may be assigned
to an intraligand * transition (Fig. 2). The fluorescence spectra of complexes
46 and the free ligand in the solid state at room temperature are presented in Fig.
3. The free ligand (L) showed an intensive emission band at 440 nm when excited
TABLE I. Photophysical data for L and complexes 16
Sample
L
1
2
3
4
5
6

Absorption
/ nm
274
292
283
283
290
264
249

Fluorescence at room temperature, / nm

Solution in MeOH
Solid state

440
413
397
426
385
411
387

395

440

442

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Fig. 2. Emission spectra of complexes 13: a) MeOH solution; b) solid state.

Fig. 3. Solid state emission spectra of ligand

(L) and complexes 46.

with light of 274 nm which might be assigned to intraligand (*) transition or

(n*) charge transfer. It is interesting that the Zn(II) complex (6) exhibited a
higher intensity than that of the free ligand L. In this case the coordination of the
ligand to the zinc ion increased the rigidity of the molecular complex and
reduced the loss of energy by radiationless thermal vibrations and hence the
emission intensity of the complex was increased. However, the emission intensities for complex 4 at 395 nm and complex 5 at 440 nm were reduced, which,
according to previous studies, could be assigned to the emission of ligand to
metal charge transfer.35,36 The quenching of fluorescence of a ligand by transition metal ions upon complexation, a rather common phenomenon, can be explained by processes such as magnetic perturbation, redox activity, and electrons.37,38 The emission bands of the free ligand showed a reduction in intensity
upon complexation and the phenomenon could be attributed to (n*) transitions

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rather than (*) transitions.39 This is due to the pairs of electrons on the free
ligand that are donated to the metal centre in the complex. The (n*) emission
intensities were therefore reduced in complexes 4 and 5.
CONCLUSIONS

When the reaction between MCl2H2O (M = Zn, Cu or Co) and L was performed in THF, complexes [ML]Cl2 (46) were obtained. In these complexes, L
acts as a tetradentate ligand leading most probably to tetrahedral stereochemistry.
In contrast to the complexes of L obtained in THF, the investigation of the reactions between MCl2xH 2O and L in ethanol led to the novel complexes
[M(L)Cl]Cl (13). In each of these three complexes, one of the two imine bands
in the parent ligand was hydrolysed on reaction with MCl2xH2O (M = Zn, Cu or
Co) and the resultant primary amine nitrogen coordinated to the metal ions in a
(possibly) pseudo-tetrahedral geometry. Work is also in progress in which this
behaviour for other similar ligands is being investigated.
Acknowledgement. Financial assistance from Alzahra University is acknowledged.

-
()trans-1,2- 2-
Cu(II), Co(II) Zn(II)
MARYAM LASHANIZADEGAN MARZIEH SARKHEIL

Department of Chemistry, Faculty of Sciences, Alzahra University, P. O. Box 1993893973, Tehran, Iran

trans-N,N-(2-)-1,2- (L). MCl2xH2O (M =

= Cu, Co Zn)
, L
N3 . L MCl2xH2O (M = Cu, Co Zn)
THF [ML]Cl2 . L [M(L)Cl]Cl [ML]Cl2
, UVVis, FT-IR 1H-NMR
GC/MS . 1H-NMR CDCl3,
DMSO .

. (*) , .
( 3. 2011, 24. 2012)

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