A trinuclear copper (II) complex derived from a chiral [3 + 3] phenol-based macrocycle: Synthesis, structure and magnetic properties

Article abstract of DOI:10.1016/j.inoche.2014.07.032

An enantiopure trinuclear Cu(II) complex of chiral phenol-based macrocyclic polyamine ligand, which is derived from the [3 + 3] condensation of 3,5-diformyl-4-hydroxyzoic acid ethyl ester with (1R,2R)-1,2-diaminocyclohexane and followed by borohydride reduction, has been synthesized and characterized. The circular dichroism (CD) spectra confirmed its structural chirality in the bulk sample. Variable temperature magnetic data indicated that there is an antiferromagnetic coupling between the metal centers in the complex.

Full text of DOI:10.1016/j.inoche.2014.07.032

Inorganic Chemistry Communications 47 (2014) 144–147
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
A trinuclear copper (II) complex derived from a chiral [3 + 3]
phenol-based macrocycle: Synthesis, structure and magnetic properties
Lin Cheng ⁎, Jun Wang , Xiu-Ying Zhang , Shao-Hua Gou a,b,⁎, Lei Fang a,b
a,b,
a
a
a
Pharmaceutical Research Center, School of Chemistry and Chemical Engineering, Southeast University, Nanjing 211189, China
Jiangsu Province Hi-Tech Key Laboratory for Bio-medical Research, Southeast University, Nanjing 211189, China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 June 2014
Received in revised form 21 July 2014
Accepted 24 July 2014
Available online 25 July 2014
An enantiopure trinuclear Cu(II) complex of chiral phenol-based macrocyclic polyamine ligand, which is derived
from the [3 + 3] condensation of 3,5-diformyl-4-hydroxyzoic acid ethyl ester with (1R,2R)-1,2-diaminocyclohexane
and followed by borohydride reduction, has been synthesized and characterized. The circular dichroism (CD) spec-
tra confirmed its structural chirality in the bulk sample. Variable temperature magnetic data indicated that there is
an antiferromagnetic coupling between the metal centers in the complex.
©
2014 Elsevier B.V. All rights reserved.
Keywords:
Trinuclear Cu(II) complex
Chiral [3 + 3] macrocycle
Circular dichroism spectra
Antiferromagnetic coupling
Recent years have witnessed an explosion of interests in the re-
search of macrocyclic complexes, not only because of their intriguing
variety of architectures and multinuclear metals, but also because of
their fascinating extraordinary properties in the fields of catalysis,
molecular recognition, metalloenzyme and magnetic materials [1].
Currently, there have been extensive studies on the synthesis and
construction of the phenol-based metal complexes based on macro-
cyclic Schiff-bases or reduced Schiff-bases, which are derived from 4-
substituted-2,6-diformyl phenols with diamines and also display
interesting magnetic, electronic, and/or catalytic properties [2–4].
Until now, a large number of homodinuclear [5] or heterodinuclear
due to their specific properties for a wide range of remarkable applica-
tions including catalysts, metal enzyme mimics and molecular-based
magnets [13]. Phenol-based chiral macrocyclic polyamine ligands have
been widely developed in the construction of chiral polynuclear metal
complexes, such as Ln(III) [10] and Zn(II) [7b,11]. Only two trinuclear
Cu(II) complexes of chiral macrocycles derived from [3 + 3] condensation
products of 1,2-trans-diaminocyclohexane and dicarbonyl compounds
have been published, which showed the presence of antiferromagnetic
coupling between the triangular metal centers [12]. As part of our ongoing
study of phenol-based macrocyclic polyamine ligands and their com-
plexes [4], we report here the synthesis [14], crystal structure [15,16]
and magnetic properties of a new chiral trinuclear Cu(II) complex,
[
2a,6] discrete complexes with this kind of symmetrical and asym-
metrical phenol-based macrocycles have been reported. However,
the synthesis of complexes containing more than two metal centers is
still in their infancies due to the easy degradation of [3 + 3], [4 + 4]
and larger macrocycles in the presence of metal ions [4b,7]. Mean-
while, the diamines mainly focused on achiral diamines, such as
ethylenediamine or diethylenetriamine and 2-hydroxy-5-methyl-
benzene-1,3-dicarbaldehyde [5,6,8], and the use of chiral diamines such
as 1R,2R-diaminocyclohexane, 1R,2R-diphenylethylenediamine,
and R-1,1-binaphthalenyl-2,2-diamine in the construction of chiral
Schiff base Robson-type macrocycles has received limited studies
[Cu
3 3 4 3 2 5
(Et-L)(OH)][Cu (Me-L)(OH)]·4ClO ·2CH OH·C H OH (1), by de-
signing a new macrocyclic ligand via the [3 + 3] condensation of
(1R,2R)-1,2-diaminocyclohexane with 3,5-diformyl-4-hydroxyzoic acid
ethyl ester and followed by borohydride reduction (Scheme 1), in
which Me-H
nol during the growth of single crystals of 1 with Et-H
in mixed methanol/water solution at room temperature.
Compared to that of Et-H L, IR spectra of complex 1 exhibit distin-
guishable variations coming from red shift of absorption peaks and a
3 3
L comes from the transesterification of Et-H L and metha-
3
L and Cu(ClO
4 2
)
3
−
1
new strong band in the 1115 cm
region which can be ascribed to
[
4b,7,9–12].
the vibration of perchlorates, suggesting that Cu(II) ions have been in-
corporated into the macrocyclic ligands [17c]. Meanwhile, the peaks of
On the other hand, considerable efforts have been directed in the last
−
1
two decades towards the research of polynuclear copper(II) complexes
2935 and 2863 cm
can be attributable to the C\H (of methylene
−
1
groups) stretching vibration [17]. The peak of 1701 cm can be attrib-
uted to the C_O (of ester groups) stretching vibration. Strong absorp-
⁎
Corresponding authors at: Pharmaceutical Research Center, School of Chemistry and
−
1
tion bands at 1304 and 1210 cm
vibration (see Fig. S3).
are due to the C\N stretching
Chemical Engineering, Southeast University, Nanjing 211189, China.
E-mail addresses: lcheng@seu.edu.cn (L. Cheng), sgou@seu.edu.cn (S.-H. Gou).
http://dx.doi.org/10.1016/j.inoche.2014.07.032
1387-7003/© 2014 Elsevier B.V. All rights reserved.

L. Cheng et al. / Inorganic Chemistry Communications 47 (2014) 144–147
145
3 3
Scheme 1. Synthesis of Et-H L and Me-H L.
Single-crystal X-ray diffraction reveals that 1 crystallizes in mono-
clinic P2 space group, with the asymmetric unit of four perchlorates,
two methanol and one ethanol molecules, as well as two similar
trinuclear Cu(II) units: [Cu (Et-L)(OH)] and [Cu (Me-L)(OH)]. The mac-
rocyclic ligands in [Cu (Et-L)(OH)] and [Cu (Me-L)(OH)] are a little
amine nitrogen atoms from the same diaminocyclohexane for each
Cu(II) and offers one bridging, two bridging, one bridging and one ter-
minal deprotonated phenol oxygen atom for Cu , Cu and Cu , respective-
1 2 3
ly, being different from the reported chiral trinuclear Cu(II) complexes of
macrocyclic amines, in which each deprotonated phenol oxygen atom
1
3
3
3
3
different, but the two trinuclear Cu(II) units have the same coordination
environments and modes of the corresponding Cu(II) ions and the
macrocyclic ligands, as well as the similar bond length and bond an-
bridges two adjacent Cu(II) atoms [12]. In [Cu
ion exhibits different geometry (Fig. 1a). Both Cu
proximate square-planar geometry, being surrounded by two adjacent
amine nitrogen atoms and two oxygen atoms. For Cu , the two oxygen
atoms come from a bridging phenoxo oxygen atom O and a bridging hy-
droxyl group; while for Cu , the two oxygen atoms originate from a bridg-
ing phenoxo oxygen atom O
Cu
adjacent amine nitrogen atoms, a bridging phenoxo oxygen atom O
3
(Et-L)(OH)], each Cu(II)
1
and Cu display an ap-
3
gles (Fig. 1 and Table S1). Thus, only the structure of [Cu
is depicted in detail. The deprotonated macrocyclic ligand in
Cu (Et-L)(OH)] shows a highly distorted, irregular saddle-shaped con-
3
(Et-L)(OH)]
1
4
[
3
3
formation, which reflects the helical twist and the considerable folding
of the macrocycle [12]. Meanwhile, the macrocyclic ligand provides two
1
and a terminal phenoxo oxygen atom O
7
.
2
is square pyramidal with the base of the pyramid defined by two
4
and a bridging hydroxyl group. The apical is occupied by another bridging
phenoxo oxygen atom O with the Cu ⋯O distance of 2.413(7) Å, which
is substantially longer than the Cu ⋯O and Cu ⋯O20 distances of
.979(6) and 1.905(7) Å, respectively, and is typical for square pyrami-
dal Cu(II) complexes (Fig. 1 and Table S1) [12]. Additionally, in the axial
positions, Cu and Cu have a very weak interaction with a perchlorate
1
2
1
2
4
2
1
2
3
and an oxygen atom from an ester group of an adjacent macrocyclic li-
gand, respectively, with the Cu⋯O distances of 2.707(8)–2.862(11) Å.
1 2 2 3
Cu and Cu , as well as Cu and Cu , are bridged by a deprotonated
phenol oxygen atom, with the Cu
.876(3) and 3.900(1) Å, as well as the Cu
gles of 95.0(3) and 132.9(3)°, respectively. Cu
a phenoxo oxygen atom and the Cu ⋯Cu distance is 4.062(4) Å. It's not-
ing that after coordination to the Cu(II) ions, the achiral nitrogen atoms N
1
⋯Cu
2
and Cu
–O –Cu and Cu
and Cu are not bridged by
2
⋯Cu
3
distances of
2
1
4
2
2
–O –Cu an-
1
3
1
3
1
3
1
and N11 of the amines in the free ligands adopt R configuration and all the
other nitrogen atoms adopt S configuration, being different from those
that we reported, in which all the nitrogen atoms adopt S configuration
after they are ligated to metal ions [17c–h]. This may be ascribed to the
folding of the macrocycles, which makes the configurations of the corre-
sponding nitrogen atoms changed in order to meet the needs of coordina-
tion to Cu(II) ions.
Phase purity of the bulky crystalline sample of 1 was confirmed by a
good match between the experimental and simulated powder X-ray dif-
fraction (PXRD) patterns, as shown in Fig. S4.
The thermogravimetric analysis of powder sample 1 was carried out
from 31 to 898 °C under nitrogen atmosphere at the heating rate of
−
1
1
3
0 °C min , as shown in Fig. S5. There is a distinct weight loss between
1 and 242 °C (expt. 2.5%, calcd. 4.0%), which shows the release of the
free methanol and ethanol molecules. Then, the weight loss of 71.4%
in a range of 242–898 °C indicates the removal of the macrocyclic li-
gands and the decomposition of the whole structure.
Circular dichroism (CD) spectroscopy is a very powerful technique
to check the chirality of bulk materials [17,18]. The chiral nature of the
3
ligand Et-H L and complex 1 was confirmed by solid state CD spectros-
copy using powdered bulk crystals in a KBr matrix (Fig. 2). The ligand
and 1 were found to display similar dichroic signals in their CD spectra
with four positive Cotton effects at frequencies of 206, 246, 273, 322 and
3 3
Fig. 1. The trinuclear Cu(II) units of [Cu (Et-L)(OH)] (a) and [Cu (Me-L)(OH)] (b) in 1.

146
L. Cheng et al. / Inorganic Chemistry Communications 47 (2014) 144–147
Acknowledgments
The authors are grateful to the financial support from National Nat-
ural Science Foundation of China (no. 21001024), the Natural Science
Foundation of Jiangsu Province (BK2011587 and BK20131289) and
the funding from Southeast University (no. 4007041121 and no.
9
207040016). The authors thank Dr Wei Xue of Sun Yat-Sen Univer-
sity for magnetic measurements.
Appendix A. Supplementary data
IR, XRD and X-ray crystallographic files in CIF format of 1. CCDC ref-
erence number: 1004400. The data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK;
Fax: (internat.) +44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
Supplementary data associated with this article can be found, in the on-
line version, at http://dx.doi.org/10.1016/j.inoche.2014.07.032. This
data include MOL file and InChiKey of the most important compounds
described in this article.
3
Fig. 2. CD spectra of Et-H L and 1 in the solid state at room temperature.
2
67 nm, as well as 216, 280, 311 and 378 nm, respectively, and three
negative Cotton effects at frequencies of 217, 263 and 295 nm, as well
as 242, 299 and 357 nm, respectively, which exhibits the chirality of
the compounds and is in agreement with the chiral space group of 1.
The magnetic properties of 1 were determined over the temperature
range 2–300 K at an applied field of 1000 Oe. Plots of magnetic suscep-
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[
[
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6 3
O amine, Dalton Trans. 41
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[
[
14] The synthesis of Et-H
adding a methanol solution (6 mL) of Et-H
O, 4 mL) of Cu(ClO ·6H O (68 mg, 0.2 mmol). The resulting blue solution
3
L was in the Supplementary materials. 1 was prepared by
3
L (182 mg, 0.2 mmol) to a solution
(H
2
4
)
2
2
was stirred for half an hour at room temperature, then filtered. The filtrate was
left evaporated in air for 3 weeks. Blue block crystals of 1 were obtained. Yield:
6
2% (56 mg) based on Cu(II).
15] Crystal data for 1: C105 152Cl
group P2 , a = 13.146(2) Å, b = 15.897(3) Å, c = 29.052(5) Å, β = 96.
H
4 6 12
Cu N O39, Mr = 2729.49, monoclinic, space
1