Novel 1D copper(II) helical chain formed by weak coordination-driven self-assembly: Synthesis, structure, and magnetic property

Article abstract of DOI:10.1002/cjoc.201100671

A novel 1D copper(II) helical chain is constructed through the connection of tetranuclear copper(II) units [Cu₄(L)(Py)₄] (H ₈L=N,N'-(BINOL-3,3'-dicarboxyl)-disalicylhydrazide, where BINOL is 1,1'-binaphthalenyl-2,2'-diol, py=pyridine) by weak coordination-driven self-assembly, and characterized by IR, single crystal X-ray diffraction, thermogravimetric analysis, and X-ray power diffraction analysis. Interestingly, the helical chains are packed in an alternating left-(M) and right-handed (P) chirality, the orientation of the helices was determined by the axial chirality of the ligand. The complex shows antiferromagnetic interactions between the copper centers.

Full text of DOI:10.1002/cjoc.201100671

FULL PAPER
DOI: 10.1002/cjoc.201100671
Novel 1D Copper(II) Helical Chain Formed by Weak
Coordination-driven Self-assembly: Synthesis,
Structure, and Magnetic Property
Huang, Wanyuna,b(黄婉云)
Chen, Zilub(陈自卢)
Zou, Huahongb(邹华红)
Liu, Dongchengb(刘冬成)
Liang, Fupei*,b(梁福沛)
a State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and
Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, China
b Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of
China), School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin, Guangxi 541004,
China
A novel 1D copper(II) helical chain is constructed through the connection of tetranuclear copper(II) units
[Cu4(L)(Py)4] (H8L＝N,N'-(BINOL-3,3'-dicarboxyl)-disalicylhydrazide, where BINOL is 1,1'-binaphthalenyl-2,2'-
diol, py＝pyridine) by weak coordination-driven self-assembly, and characterized by IR, single crystal X-ray dif-
fraction, thermogravimetric analysis, and X-ray power diffraction analysis. Interestingly, the helical chains are
packed in an alternating left-(M) and right-handed (P) chirality, the orientation of the helices was determined by the
axial chirality of the ligand. The complex shows antiferromagnetic interactions between the copper centers.
Keywords helical structures, copper, weak coordination-driven, axial chirality, magnetic property
Introduction
proven to be fruitful in the construction of fascinating
polynuclear metal complexes with various applications,
such as potential magnetic material, selective recogni-
tion, and asymmetric catalysis.[22-29] Very recently, we
have constructed a novel interesting copper(II) com-
plex[30] using a ligand, (N,N'-(2,6-pyridine-dicarboxyl)-
disalicyl-hydrazide), which containes two salicylhy-
drazide groups. As part of our ongoing study of metal
complexes constructed by two or more salicylhydrazide
groups, introducing the N-acylsalicylhydrazide func-
tional group in the 3-position of the binaphthyl scaffold
as building blocks has particularly attracted our interest.
We designed and synthesized a ligand containing
bis-salicylhydrazide based binaphthyl framework, N,N'-
Over the last few years, considerable effort has been
devoted to design and syntheses of new building blocks
to construct helical structure especially chiral helical co-
ordination polymers due to their aesthetically appealing
topologies and potential applications in nonlinear opti-
cal materials, chiral recognitions, asymmetric catalysis
and host-guest interactions.[1-9] The control of helicity at
the supramolecular level via inducing conformation re-
strictions of molecules, formation of molecular hydro-
gen bonds, or coordination to metal ions is a particularly
fascinating challenge.[10] Regarding the control of helic-
ity, axially asymmetric 1,1'-binaphthyl backbone is an
interesting building blocks.[11] Both Lin’s and Hong’s
group have designed a variety of chiral bridging ligands
based on atropisomeric 1,1'-binaphthyl framework and
have constructed some novel helical metal-organic
complexes with promising applications.[12-16] Interest-
ingly, extensive investigations showed that binaphthyl-
based materials and catalysts were often substituted at
the 2-, 4-, 5- or 6-position to achieve additional mo-
lecular connecting points,[17-20] the 3-position of the
binaphthyl scaffold has received much less attention.[21]
On the other hand, the N-acyl-salicylhydrazide
ligands with multiple N, O coordination sites have been
(BINOL-3,3'-dicarboxyl)-disalicylhydrazide
(H8L),
which features hinge-like ditopic with conformational
and geometrical flexibility, where BINOL is 1,1'-
binaphthalenyl-2,2'-diol. Herein, we present the synthe-
sis and structure of one copper(II) complex with H8L
ligand, [Cu4(L)(Py)4]•1.5DMF (1). A novel 1D helical
chain was constructed with the aid of weak coordina-
tion-driven self-assembly. More interestingly, the heli-
cal chains are packed in an alternating left-(M) and
right-handed (P) chirality, each chain is composed of
only Ra or only Sa enantiomers ligand. The magnetic
properties of the complex 1 were investigated.
*
E-mail: fliangoffice@yahoo.com; Tel.: 0086-0773-5856302; Fax: 0086-0773-5832294
Received December 9, 2011; accepted February 12, 2012; published online May 7, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201100671 or from the author.
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Chin. J. Chem. 2012, 30, 1052—1056

Novel 1D Copper(II) Helical Chain Formed by Weak Coordination-driven Self-assembly
Experimental
(0.0306 g, 0.15 mmol) were dissolved in 10 mL DMF,
subsequently 0.5 mL pyridine was added. The mixture
was stirred for 10 h at room temperature and then fil-
tered. The filtrate was allowed to evaporate at room
temperature, giving dark green block crystals of 1 suit-
able for single crystal X-ray diffraction after one month
in 65% yield (based on Cu). IR data (KBr) ν: 3430 (s),
1603 (s), 1583 (m), 1520 (s), 1449 (m), 1420 (m), 1366
Materials and general methods
All chemicals were used as obtained without further
purification. 2,2'-Dihydroxy-[1,1']binaphthalenyl-3,3'-
dicarboxylic acid (BINOL-3,3'-diacid) was prepared
according to the literature method.[31] Infrared spectra
were recorded as KBr pellets using a Nicolet 360 FT-IR
spectrometer. Elemental analyses (C, H and N) were
－
1
(m), 1315 (s), 1257 (m), 1217 (m), 754 (s), 696 (s) cm .
Anal. calcd for C60.5H48.5Cu4N9.5O9.5 (%): C 55.26, H
3.72, N 10.12; found C 55.07, H 3.98, N 10.44.
performed on a Vario EL analyser. H NMR and 13C
1
NMR spectra were recorded on a Bruker AVANCE 500
spectrometer in DMSO-d6 with TMS as an internal
standard. Thermogravimetric analyses were recorded
with a Perkin-Elmer Pyris Diamond TG analyzer at a rate
of 10 ℃/min from room temperature to 990 ℃ under a
nitrogen atmosphere. The powder X-ray diffraction
(PXRD) data were collected on a Rigaku D/max 2200
diffractometer with Cu-Kα radiation. The magnetic sus-
ceptibility measurements were carried out on polycrystal-
line samples using a Quantum Design MPMS-5 SQUID
magnetometer in the temperature range 2—300 K and
magnetic field up to 5 T. Diamagnetic corrections were
estimated from Pascal’s constants.
X-ray crystallography
Suitable single crystal of complex 1 was selected and
mounted onto thin glass fibers, and the measurement was
performed at 185(2) K using a Bruker CCDArea Detector
with graphite-monochromated Mo-Kα radiation (λ ＝
0.71073 Å). The structure was solved by direct methods
using the SHELXS-97 program package and refined
against F2 by full-matrix least-squares methods with
SHELXL-97[32,33] with anisotropic thermal parameters for
all the non-hydrogen atoms except the disorder guest
DMF. The hydrogen atoms were introduced into the
geometrically calculated positions and refined riding on
the corresponding parent atoms, except those bound to
the disorder DMF. The crystallographic data are summa-
rized in Table 1, and the selected bond lengths and angles
are listed in Table 2.
Preparation of ligand (H8L)
The mixture of 3.74 g (10 mmol) BINOL-3,3'-diacid
and 50 mL SOCl2 was refluxed in an 80 ℃ oil bath un-
der nitrogen atmosphere for 10 h. Then the excess SOCl2
was removed under vacuum. The crude carbonyl chloride,
as a yellow foaming solid, was then dissolved in 30 mL
dry THF and used in the next step immediately.
Triethylamine 2.9 mL (20 mmol) was added to 3.04 g
(20 mmol) 2-hydroxy-benzoic acid hydrazide in 40 mL
dry THF and the mixture was stirred in a －10 ℃ cool
bath for 20 min. Then the crude carbonyl chloride pre-
pared in the forward step was added to it dropwise and the
mixture was stirred in the cool bath for another 1 h and
then at room temperature for 48 h. Then crude product
was deposited and filtrated. The solid was washing fully
with water (20 mL×2) and THF (20 mL×2). The further
purification could be carried out by reflux of the crude
product in 40 mL mixture of THF and acetone for 20 min
and hot filtration immediately. The yellow solid was col-
Table 1 Crystal data and structure refinement parameters for
complex 1
Formula
C121H97Cu8N19O19
Formula weight
2629.50
185(2)
Temperature/K
Crystal system
Monoclinic
C2/c
Space group
a/Å
30.893(3)
14.3503(12)
25.076(2)
90
b/Å
c/Å
α/(°)
β/(°)
γ/(°)
1
lected and dry, yield 63%. m.p.＞300 ℃; H NMR
101.855(2)
90
(DMSO, 500 MHz) δ: 11.79 (s, 2H, NH), 11.58 (s, 2H,
NH), 11.46 (s, 2H, Ar-OH), 10.89 (s, 2H, Ar-OH), 8.83 (s,
2H, ArH), 7.95—8.01 (m, 4H, ArH), 7.39—7.49 (m, 6H,
ArH), 6.96—7.02 (m, 6H, ArH); 13C NMR (DMSO,
125.77 MHz) δ: 168.43, 167.05, 158.79, 153.74, 135.85,
134.35, 129.72, 129.59, 129.13, 128.88, 126.79, 124.12,
124.03, 119.37, 117.43, 116.77, 115.94, 115.05; IR (KBr)
ν: 3217 (s), 1608 (s), 1561 (m), 1481 (s), 1454 (w), 1353
(m), 1307 (m), 1238 (w), 1212 (w), 1158 (m), 785 (w),
Z
4
V/Å3
－
Density/(g•cm )
10879.7(16)
1.605
3
µ/mm－
1.613
1
F(000)
5360
Reflections collected
Independent reflections
Rint
31868
－
－
9524
1
753 (s) cm ; ESI-MS: M－H peak at m/z 641.10. Anal.
calcd for C36H26N4O8: C 67.29, H 4.08, N 8.72; found C
67.53, H 4.15, N 8.99.
0.0736
GOF on F2
0.968
R1, wR2 (I＞2σ(I))
R1, wR2 (all data)
0.0539/0.1243
0.1123/0.1414
Preparation of [Cu4(L)(Py)4]•1.5 DMF (1)
H8L (0.0322 g, 0.05 mmol) and Cu(OAc)2•H2O
Chin. J. Chem. 2012, 30, 1052—1056
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Huang et al.
FULL PAPER
Table 2 Selected bond lengths (Å ) and angles (°) for complex 1a
Cu(1)—O(1)
1.873(3)
Cu(2)—N(8)
1.977(4)
1.986(3)
1.872(4)
1.984(3)
2.776
Cu(3)—O(4)
1.895(3)
Cu(1)—N(1)
1.869(4)
Cu(2)—O(6)
Cu(3)—N(3)
1.979(5)
Cu(1)—O(3)
1.955(3)
Cu(3)—N(2)
Cu(4)—N(5)
1.870(4)
Cu(1)—N(4)
1.983(4)
Cu(3)—O(2)
Cu(4)—O(7)
1.952(4)
Cu(2)—N(6)
1.892(4)
Cu(3)—O(8A)
Cu(3B)—O(8)
N(6)-Cu(2)-N(8)
O(8)-Cu(2)-N(8)
N(6)-Cu(2)-O(6)
O(8)-Cu(2)-O(6)
O(4)-Cu(3)-N(3)
N(2)-Cu(3)-O(4)
N(2)-Cu(3)-N(3)
N(3)-Cu(3)-O(2)
Cu(4)—N(7)
1.982(4)
Cu(2)—O(8)
1.913(4)
2.776
Cu(4)—O(5)
1.865(4)
O(1)-Cu(1)-N(1)
O(1)-Cu(1)-O(3)
N(1)-Cu(1)-O(3)
O(1)-Cu(1)-N(4)
N(1)-Cu(1)-N(4)
O(3)-Cu(1)-N(4)
N(6)-Cu(2)-O(8)
N(8)-Cu(2)-O(6)
92.24(15)
172.15(14)
82.17(15)
92.38(15)
168.00(16)
94.18(15)
91.68(17)
94.80(17)
175.93(19)
92.33(18)
81.19(16)
172.87(15)
92.75(17)
91.52(16)
174.64(17)
94.17(16)
N(5)-Cu(4)-N(7)
O(7)-Cu(4)-N(7)
O(5)-Cu(4)-N(7)
N(2)-Cu(3)-O(2)
O(4)-Cu(3)-O(2)
O(5)-Cu(4)-N(5)
O(5)-Cu(4)-O(7)
N(5)-Cu(4)-O(7)
170.44(18)
94.58(17)
92.14(17)
81.24(15)
170.66(15)
92.25(16)
171.66(15)
81.85(16)
a Symmetry codes: A) 0.5－x, －0.5＋y, 0.5－z; B) 0.5－x, 0.5＋y, 0.5－z; C) －x, y, －z＋0.5.
one nitrogen atom [N(4)/N(7)] of a pyridine molecule to
form a slightly distorted square planar coordination
polyhedron. Similarly, Cu(2) binds to one Nbenzyl-acylamide
atom [N(6)], one OBINOL-acylamide atom [O(6)] and one
Ophenolic atom [O(8)] from one ligand and one nitrogen
atom [N(8)] of a pyridine molecule to form a slightly
distorted square planar coordination polyhedron. Cu(3)
possesses a standard square pyramid geometry with one
Nbenzyl-acylamide atom [N(2)], one OBINOL-acylamide atom
[O(2)] and one Ophenolic atom [O(4)] from one ligand and
one nitrogen atom [N(3)] of a pyridine molecule in the
equatorial plane, and one Ophenolic atom [O(8A)] from
the ligand of another tetranuclear unit at the apical posi-
tion. The geometrical parameter τ is 0.066, τ＝(α－
β)/60º, in which β and α are the bond angles that involve
trans donor atoms in the basal plane.[34] The length of
the weak coordination bond Cu(3)—O(8A) is 2.776 Å,
which is consistent with the reported copper(II) com-
plexes.[35] Connected by the weak coordination of phe-
nolic oxygen atoms [O(8) and O(8A)] with copper ions
[Cu(3) and Cu(3A)], the tetranuclear unit forms
one-dimensional helical chain along b direction as
shown in Figure 3. Each helix contains two
[Cu4(L)(Py)4] motifs with a pitch of 14.35 Å. The heli-
Results and Discussion
The ligand N,N'-(BINOL-3,3'-dicarboxyl)disalicyl-
hydrazide (H8L) was synthesized by the acylation of
racemic BINOL-3,3'-diacid and salicylhydrazide. The
ligand contains twelve potential coordinating sites from
two salicylhydrazide moieties and two phenol of the
BINOL group, and might coordinate in a octa-anionic
dodecadentate mode to metal ions. Indeed, the complex
1 was readily obtained in good yield by the reaction of
H8L with the Cu(OAc)2•H2O in a 1∶3 molar ratio
under basic condition at room temperature. As depicted
in Figure 1, the ligand uses all of its twelve coordinating
atoms to coordinate with four copper ions in a μ4-η3∶
η3∶η3∶η3 mode. The same product was obtained when
Cu(ClO4)2•6H2O or CuCl2•2H2O were used instead of
Cu(OAc)2•H2O.
O
Cu
O
C
N
N
O
O
O
Cu
Cu
O
O
N
C
O
N
Cu
Figure 1 The coordination mode of H8L ligand in 1.
Structure description
The asymmetric unit of 1 contains three four-coor-
dinated [Cu(1), Cu(2), Cu(4)] and one five-coordinated
[Cu(3)] copper ions, one ligand, four coordinated pyri-
dine molecules and one point five DMF solvent mole-
cules as shown in Figure 2. Cu(1) and Cu(4) show simi-
lar binding mode, bound to one Obenzyl-acylamide atom
[O(3)/O(7)], one NBINOL-acylamide atom [N(1)/N(5)] and
one OBINOL-phenolic atom [O(1)/O(5)] from one ligand and
Figure 2 The ORTEP drawing of 1 with thermal ellipsoids set
to 30% probability level. All H atoms and the DMF molecules are
omitted for clarity.
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Chin. J. Chem. 2012, 30, 1052—1056

Novel 1D Copper(II) Helical Chain Formed by Weak Coordination-driven Self-assembly
－
1
cal chains are packed in an alternating left-(M) and
right-handed (P) chirality in the overall structure (Figure
4). Interestingly, the right helical chain is composed of
only Sa enantiomers and the left helical chain is com-
posed of only Ra enantiomers, which demonstrate the
orientation of the helices was determined by the axial
chirality of the ligand. The aromatic rings are not
stacked, van der Waals force contributes to the stabiliza-
tion of the helical structure.
value of product χmT is 1.64 cm3•K•mol at 300 K
(Figure 5), which is slightly larger than the expected
－
value of 1.50 cm3•K•mol for four noninteracting S＝
1/2 CuII centers with a g value of 2.[36] Upon cooling,
the χmT value decreases continuously, reaching a value
of 0.0068 cm3•K•mol－1 at 2.0 K, indicating the presence
of an antiferromagnetic coupling.[37,38] The shape of the
χmT vs. T plot indicates an overall, moderate anti-
ferromagnetic coupling between the metal centers. The
Curie tail in the low temperature susceptibility data re-
veals the presence of trace amount of paramagnetic im-
purities. The antiferromagnetic nature of complex is
further supported by M vs. H plot at 2 K. The magneti-
zation is 3.626 μB per Cu4 formula unit at 5 T, which is
smaller than the saturated value of four Cu(II) ions (the
inset of Figure 5). Furthermore, the best linear fit ac-
cording to the Curie-Weiss law χm＝C/(T－θ) in the tem-
perature range of 120—300 K yields Curie constant of
1
－
2.957 cm3•K•mol and a Weiss constant of －232.485
K (Figure S3), which suggestes the presence of anti-
ferromagnetic coupling in 1. The magnetic interactions
between the adjacent two dinuclear copper(II) centers in
the Cu4 formula unit are presumed to be very weak be-
cause the bridging binaphyl group can not transmit
magnetic exchange effectively. Therefore, the tempera-
ture-variable magnetic susceptibility data can be de-
scribed by the modified Bleaney-Bowers equation (1)
for a dinuclear CuII (S1＝S2＝1/2) system.[39,40]
1
Figure 3 One dimensional helical chain viewed along the b
direction, all H atoms and pyridine are omitted for clarity.
－
1
χm＝[NAμ2g2/3KB(T－θ)][1＋1/3×exp(－2J/KBT)] ×
(1－ρ)＋NAμ2g2/4KBT＋Na
(1)
where NA is the Avogadro constant, μ the Bohr magne-
ton, KB the Boltzmann constant, g the g factor, and J the
coupling constant. NA and g have been fixed as 110×
－
10－ cm3•mol and 2.20, respectively. The best data
fits (solid red lines) with Eq. (1) for the complex 1 was
shown in Figure 5. The calculated values are 2J＝－122
6
1
－
1
cm , g＝2.01, θ＝－3 K, and ρ＝0.015, which show
that there are antiferromagnetic interactions between the
copper metal ions in the complex.[41]
Figure 4 Alternately left-(M) and right-handed (P) helix array
of 1 in bc plane.
Thermogravimetric analysis and PXRD
The thermogravimetric analysis (TGA) was carried
out to examine the thermal stability of 1. The TG curves
for 1 show its decomposition in two stages (Figure S1).
The first weight loss of 19.65% in the temperature range
of 30—197 ℃ corresponds to the loss of guest DMF
and two coordinated pyridine molecules (calcd 20.36%).
Further heating leads to the final collapse of the tetranu-
clear skeleton by the decomposition of the ligand. In
addition, the PXRD experiment is done in parallel beam
mode, which is consistent with the simulated spectrum
(Figure S2).
Magnetic properties
Figure 5 Temperature dependence of the magnetic susceptibil-
ity of 1 measured at 1000 Oe. The solid lines represent the theo-
retical fits (see text). Inset: the field dependence of the magneti-
zation at 2 K.
Magnetic susceptibility measurements were per-
formed on microcrystalline samples of the compound at
0.1 T field in the temperature range 2—300 K. The
Chin. J. Chem. 2012, 30, 1052—1056
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Huang et al.
FULL PAPER
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Conclusions
In summary, the first ligand by introducing the
N-acyl-salicylhydrazide multiple functional group in the
binaphthyl scaffold, N,N'-(BINOL-3,3'-dicarboxyl)-
disalicylhydrazide (H8L), was synthesized. Reaction of
the ligand with Cu(OAc)2•H2O under conventional con-
dition afforded a copper coordination polymer with
tetranuclear copper(II) units [Cu4(L)(py)4] as secondary
building blocks. The connection of the tetranuclear units
by weak coordination-driven self-assembly formed in-
teresting helical chain, which are composed of only Ra
or only Sa enantiomers in each case, namely the orienta-
tion of the helices was determined by the axial chirality
of the ligand. The complex shows antiferromagnetic
coupling interaction among the copper centers.
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Supplementary material
TG curve, PXRD plot, 1/χm vs. T plot and all spectra
of new compounds (Figure S1—S7) are in the support-
ing information. CCDC-855713 contains the supple-
mentary crystallographic data for complex 1. The data
can be obtained free of charge via the Internet at
http://www.ccdc.cam.ac.uk/conts/retrieving.html
or
from the Cambridge Crystallographic Data Centre
(CCDC), 12Union Road, Cambridge CB21EZ, UK.
Email: deposit@ccdc.cam.ac.uk.
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Aknowledgement
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This work was supported by the National Natural
Science Foundation of China (No. 20971029) and
Guangxi
Natural
Science
Foundation
(Nos.
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