A (3,14)-connected three-dimensional metal-organic framework based on the unprecedented enneanuclear copper(ii) cluster [Cu9(μ3- OH)4(μ2-OH)2]

Article abstract of DOI:10.1039/c3ce41086b

A hydrothermal reaction of Cu(NO₃)₂, 1,2-bis(1,2,4-triazol-1-yl)ethane (bte) and 5-sulfoisophthalate (sip) yields an interesting three-dimensional metal-organic framework {[Cu₉(OH) ₆(bte)₂(sip)₄(H₂O) ₃]·6H₂O}_n (1). A single-crystal analysis revealed that compound 1 consists of a (3,14)-connected three-dimensional MOF with a point symbol of (3·4²)₄(3 ⁸·4¹⁴·5¹⁶·6 ⁴⁰·7⁹·8⁴) based on the unprecedented enneanuclear copper(ii) cluster [Cu₉(μ₃- OH)₄(μ₂-OH)₂]. The [Cu₉(μ ₃-OH)₄(μ₂-OH)₂] enneanuclear copper(ii) cluster can be described as consisting of two [Cu₄(μ ₃-OH)₂] moieties connected to a centrally placed Cu(ii) ion (Cu1) through two μ₂-OH groups. 1 shows dominant antiferromagnetic coupling interactions and good photocatalytic activity for the degradation of methyl orange.

Full text of DOI:10.1039/c3ce41086b

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A (3,14)-connected three-dimensional metal–organic
framework based on the unprecedented enneanuclear
copper(II) cluster [Cu9(μ3-OH)4(μ2-OH)2]†
Cite this: CrystEngComm, 2013, 15,
9154
*
Xia Zhu, Shan Zhao, Yan-Fen Peng, Bao-Long Li and Bing Wu
A hydrothermal reaction of Cu(NO3)2, 1,2-bis(1,2,4-triazol-1-yl)ethane (bte) and 5-sulfoisophthalate (sip) yields an
interesting three-dimensional metal–organic framework {[Cu9(OH)6(bte)2(sip)4(H2O)3]·6H2O}n (1). A single-crystal
analysis revealed that compound 1 consists of a (3,14)-connected three-dimensional MOF with a point symbol of
(3·42)4(38·414·516·640·79·84) based on the unprecedented enneanuclear copper(II) cluster [Cu9(μ3-OH)4(μ2-OH)2].
The [Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) cluster can be described as consisting of two [Cu4(μ3-OH)2] moi-
eties connected to a centrally placed Cu(II) ion (Cu1) through two μ2-OH groups. 1 shows dominant antiferromag-
netic coupling interactions and good photocatalytic activity for the degradation of methyl orange.
Received 10th June 2013,
Accepted 10th September 2013
DOI: 10.1039/c3ce41086b
www.rsc.org/crystengcomm
Introduction
been synthesized,10 no [Cu9(μ3-OH)4(μ2-OH)2] enneanuclear
copper(II) cluster has been observed.
The crystal engineering of metal–organic frameworks (MOFs)
has received a great deal of attention because of their various
architectures and topologies as well as their potential applica-
tion in the fields of magnetism, gas storage, molecular
adsorption, molecular recognition and catalysis.1 To design
and synthesize MOFs with a unique structural diversity, it
would be highly desirable to choose organic ligands with ideal
coordination modes. Flexible bidentate N-donor ligands, such
as bis(imidazole)2 and bis(triazole)3 ligands, are widely used to
construct coordination polymers because flexible ligands
can adopt different conformations according to the geometric
needs of the different metal ions.
Polynuclear copper(II) complexes have been of interest in
recent years because several unusual metalloenzymes contain
copper clusters.4,5 Multicopper oxidases (e.g., ascorbate oxi-
dase and laccase) contain a trinuclear cluster core, [Cu3(OH)]
or [Cu3(O)], and thus have generated an extreme interest in
the synthesis of triangular copper complexes having similar
structural cores.4–9 Many compounds containing a [Cu3(μ3-OH)]
core have been synthesized and magnetically characterized.6–9
Several compounds containing [Cu4(μ3-OH)2] tetranuclear or
[Cu5(μ3-OH)2] pentanuclear copper(II) clusters have also been
obtained.8,9 Although few enneanuclear copper(II) clusters have
Methyl orange is one of the most stable azo dyes, which
are extensively used in the textile industry and are resistant
to biodegradation. Decomposition of such dye molecules into
some simple molecules can diminish the environment pollu-
tion caused by them. A new application of metal–organic
frameworks (MOFs) is photocatalysis and some results have
demonstrated that MOFs are efficient photocatalysts for the
degradation of organic dyes.11–13
We have previously synthesized many MOFs with structural
diversity using flexible imidazole and triazole ligands.14,15
A
two-dimensional MOF {[Cu5(bime)(μ3-OH)2(phth)4](H2O)2}n
based on pentanuclear copper(II) clusters [Cu5(μ3-OH)2(phth)4]
was synthesized by the hydrothermal reaction of CuSO4,
1,2-benzenedicarboxylate (phth) and 1,2-bis(imidazol-1-yl)ethane
(bime).14 Herein, we report
a
(3,14)-connected three-
dimensional MOF {[Cu9(OH)6(bte)2(sip)4(H2O)3]·6H2O}n (1)
(bte = 1,2-bis(1,2,4-triazol-1-yl)ethane, sip = 5-sulfoisophthalate)
based on the unprecedented enneanuclear copper(II) cluster
[Cu9(μ3-OH)4(μ2-OH)2]. 1 shows dominant antiferromagnetic
coupling interactions. 1 not only exhibits good photocatalytic
activity for the degradation of a methyl orange (MO) solution
under UV light irradiation but is also very stable and easily sep-
arated from the reaction system for reuse.
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry,
Chemical Engineering and Materials Science, Soochow University, Suzhou 215123,
PR China. E-mail: libaolong@suda.edu.cn
Experimental section
Materials and physical measurements
† Electronic supplementary information (ESI) available: Selected bond lengths
and angles, hydrogen bonding, additional figures for the crystal structures and
PXRD pattern. CCDC 928643. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/c3ce41086b
All reagents were of analytical grade and used without fur-
ther purification. Elemental analyses for C, H and N were
performed on a Perkin-Elmer 240C analyzer. IR spectra
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were obtained using KBr pellets on a Nicolet 170SX FT-IR
spectrophotometer in the 4000–400 cm−1 region. Variable-
temperature magnetic susceptibilities were measured with a
MPMS-7 SQUID magnetometer. Diamagnetic corrections were
made using Pascal's constants for all constituent atoms.
EPR spectra were recorded on a Bruker EMX-10/12 instru-
ment. X-ray powder diffractions (XRPD) were performed on a
D/MAX-3C diffractometer with Cu–Kα radiation (λ = 1.5406 Å)
at room temperature.
framework based on the unprecedented enneanuclear
copper(II) cluster [Cu9(μ3-OH)4(μ2-OH)2]. The [Cu9(μ3-OH)4(μ2-OH)2]
enneanuclear copper(II) cluster can be described as consisting
of two [Cu4(μ3-OH)2] moieties connected to a centrally placed
Cu(II) ion (Cu1) through two μ2-OH groups with a Cu1⋯Cu2
distance of 2.9793(3) Å (Fig. 1). Thus, the central Cu1 lies on a
crystallographic inversion center. The distorted square coordi-
nation geometry of the central copper(II) ion, Cu1, is a CuO4
chromophore through two carboxylate oxygen atoms (O1, O1A)
and two μ2-OH groups (O15, O15A) (Fig. S1 in the ESI†).
The Cu1–O15–Cu2 bond angle is 101.993(7)°.
Synthesis of compound 1
In the [Cu4(μ3-OH)2] moiety, Cu2 has a square-pyramidal
geometry with a CuO5 chromophore and is coordinated by
two carboxylate oxygen atoms (O2, O8B) and one sulfo oxygen
atom (O12) from three sip ligands and two μ3-OH groups
(O15, O16) (Fig. S2 in the ESI†). The Cu2 ion lies 0.151(2) Å
over the plane defined by the basal donor atoms (O2/O15/
O8B/O16). The apical site is occupied by a sulfo oxygen atom
(O12) with an elongated Cu–O bond length of 2.269(5) Å. The
square-pyramidal (4 + 1) coordination geometry of the Cu3
and Cu4 ions are coordinated by one carboxylate oxygen
atom (O11C or O3F) and one sulfo oxygen atom (O5G or O12)
from two sip ligands, two μ3-OH groups (O15, O16) and one
triazole nitrogen atom from one bte ligand (N6D or N3) and
lie 0.039(2) and 0.071(2) Å, respectively, over the plane
defined by their basal donor atoms (O11C/O17/O16/N6D and
O3F/O16/O17/N3) (Fig. S3 and Fig. S4 in the ESI†). The apical
sites of the Cu3 and Cu4 atoms are occupied by a sulfo oxy-
gen atom (O5G and O12) with an elongated Cu–O bond
length of 2.498(7) and 2.432(5) Å, respectively. The τ values of
Cu2, Cu3 and Cu4 are 0.008, 0.062 and 0.133, respectively.
Therefore, the coordination structure of the Cu3 atom has
more distortion than that of the Cu2 site. The coordination
structure of the Cu4 atom has the most distortion. Cu5 is
coordinated by two carboxylate oxygen atoms from two sip
ligands (O4E, O10C), one μ3-OH group (O17) and disordered
water molecules (O18, O19, O20, O21) (Fig. S5 in the ESI†).
One μ3-OH group (O16) connects three Cu ions (Cu2, Cu3,
Cu4) and deviates from the Cu atoms plane over 0.756(2) Å
(Fig. 1). The Cu2–O16–Cu3, Cu3–O16–Cu4 and Cu2–O16–Cu4
bond angles are 114.368(5), 95.016(7) and 108.659(7)°, respec-
tively. The other μ3-OH group (O17) also connects three
Cu ions (Cu3, Cu4, Cu5) and deviates from the Cu atom
plane down 0.650(2) Å. The Cu3–O17–Cu4, Cu3–O17–Cu5 and
Cu4–O17–Cu5 bond angles are 93.926(7), 120.254(7) and
113.877(5)°, respectively. Two μ3-OH groups (O16, O17)
A solution of NaH2sip (0.40 mmol) in 10 mL of H2O was
adjusted to
a pH = 6 with NEt3 and Cu(NO3)2·3H2O
(1.50 mmol) was added with stirring. Then, bte (0.20 mmol)
dissolved in 10 mL of EtOH was added. The mixture was
added to a 30 mL Teflon-lined stainless autoclave and this
was sealed and heated to 130 °C for 5 days and then cooled
to room temperature. Blue block-shaped crystals were col-
lected. Yield: 0.056 g (26% based bte). Anal. calcd. for
C44H52Cu9N12O43S4 (compound 1): C, 24.73; H, 2.45; N,
7.87%. Found: C, 24.67; H, 2.41; N, 7.83. IR data (cm−1):
3734w, 3572br, 3121w, 1620s, 1588s, 1454s, 1377s, 1315m,
1288m, 1231s, 1177s, 1134m, 1107w, 1042m, 999m, 937w,
922w, 891w, 802w, 772m, 729m, 679w, 632w, 444w.
X-ray crystallography
A single crystal of compound 1 suitable for X-ray crystallogra-
phy was carefully selected under an optical microscope and
glued to thin glass fibers. The diffraction data were collected
on a Rigaku Saturn CCD diffractometer with graphite mono-
chromated MoKα radiation (λ = 0.71075 Å). Intensities were
collected using the ω scan technique. The structures were
solved by direct methods and refined with the full-matrix
least-squares technique (SHELXTL-97).16 The hydrogen atom
positions for the bte and sip ligands were determined using
a theoretical calculation and were included in the final
refinement according to the riding model approximation.
Photocatalytic reactions
The experiment was carried out in a typical process. Com-
pound 1 (0.050 g) was added into 200 mL of a methyl orange
(MO) solution (10 mg L−1). The suspension solution was
stirred in the dark for about 30 min, respectively. Then, the
mixture was stirred continuously under UV irradiation from
a 175 W high pressure mercury vapour lamp (main output
365 nm). At a given interval, aliquots of the reaction mixture
were periodically taken and analyzed with a UV-vis spectro-
photometer at an absorption wavelength of 506 nm. This
procedure was repeated in the absence of 1 as a blank com-
parison experiment.
separate the Cu ions and generate
a
tetranuclear
[Cu4(μ3-OH)2] moiety with a chair arrangement with the
Results and discussion
Crystal structure
A single-crystal analysis17 revealed that compound 1 consists
of
a
(3,14)-connected three-dimensional metal–organic
Fig. 1 The [Cu9(μ3-OH)6] enneanuclear copper(II) cluster of compound 1.
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Cu⋯Cu separations in the range of 2.9019(3)–3.4256(3) Å
(Cu2⋯Cu3, 3.3313(3) Å; Cu2⋯Cu4, 3.1987(3) Å; Cu3⋯Cu4,
2.9019(3) Å; Cu3⋯Cu5, 3.4256(3) Å; Cu4⋯Cu5, 3.2967(3) Å).
The noncentrosymmetric tetranuclear [Cu4(μ3-OH)2] moiety in
1 is similar to that in [Cu4(OH)2(tr2ad)2(H-adtc)2(H2O)2]·3H2O
(tr2ad
=
1,3-bis(1,2,4-triazol-4-yl)adamantane, H4-adtc
=
1,3,5,7-adamantanetetracarboxylic acid).8a The copper atoms in
1 are all in the +II oxidation state, confirmed by their
coordination geometries and BVS calculations.18
There are two kinds of sip ligands in compound 1. One car-
boxylate group (O1, O2) of a sip ligand has a bidentate coordi-
nation mode bridging two Cu(II) ions (Cu1 and Cu2) of one
tetranuclear Cu(II) cluster. The other carboxylate (O3, O4)
shows a bidentate coordination mode bridging two Cu(II) ions
(Cu4F and Cu5F) of the second tetranuclear Cu(II) cluster. The
sulfo group (O5, O6, O7) has a monodentate coordination
mode bonding to a Cu(II) ion (Cu3E) of the third tetranuclear
Cu(II) cluster (Fig. 2). One carboxylate group (O8, O9) of the
other sip ligand has a monodentate coordination mode
connecting one Cu(II) ion (Cu2B) of one tetranuclear Cu(II)
cluster. The other carboxylate (O10, O11) shows a bidentate
coordination mode bridging two Cu(II) ions (Cu5H and Cu3H)
of the second tetranuclear Cu(II) cluster. The sulfo group
(O12, O13, O14) has a bidentate coordination mode linking
two Cu(II) ions (Cu2 and Cu4) of the third tetranuclear Cu(II)
cluster (Fig. 3).
Fig. 3 The coordination mode of the other sip ligand in compound 1. Symmetry
transformations used to generate equivalent atoms: B −x,−y + 1,−z + 1; H −1/2 + x,
3/2 − y, 1/2 + z.
All the sip ligands are 3-connected and connect three
[Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) clusters. Each
[Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) cluster con-
nects 12 sip ligands (Fig. 4). Each bte ligand shows the
gauche-conformation and connects the Cu3 and Cu4 atoms
with a distance of 8.834(2) Å. Each [Cu9(μ3-OH)4(μ2-OH)2]
enneanuclear copper(II) cluster links two identical clusters
through two double bte ligands (Fig. 5). The enneanuclear
copper(II) clusters are bridged by the sip and bte ligands to
construct an unusual three-dimensional metal–organic
framework. The 3D network is very complicated.
Fig. 4 A [Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) cluster connects 12 sip
ligands.
Topologically, the [Cu9(μ3-OH)4(μ2-OH)2] enneanuclear
copper(II) cluster is simplified as one node which is 14-
connected (Fig. 6). The sip is a 3-connected node. Double bte
Fig. 5 Each [Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) cluster connects two
identical enneanuclear copper(II) clusters through two double bte ligands in
compound 1.
ligands show as 2-connected. The complicated 3D network
can be described as a (3,14)-connected 3D network (Fig. 7).
The ratio of the 3-connected sip ligand and 14-connected
copper(II) cluster is 4 : 1. The point symbol of the 3D network
is (3·42)4(38·414·516·640·79·84).19 Such a (3,14)-connected 3D
network has not been reported so far, to the best of our
knowledge.19d
Fig.
2
The coordination mode of one sip ligand in compound 1 (symmetry
transformations used to generate equivalent atoms: D x + 1, y, z; G 1/2 + x, −y + 3/2,
z + 1/2).
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Fig. 6 The 14-connected [Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) cluster.
The red and turquoise balls show the 3-connected sip ligands and 14-connected
[Cu9(μ3-OH)4(μ2-OH)2] enneanuclear copper(II) clusters, respectively. The blue sticks
represent the 2-connected double bte ligands.
Fig. 8 Plot of μeff vs. T for compound 1.
Fig. 9 Plot of 1/χM vs. T for compound 1 (the solid line represents a Curie–Weiss
fit in the temperature range of 60–300 K).
Fig. 7 Schematic of the (3,14)-connected 3D network in 1. The red and turquoise
balls show the 3-connected sip ligands and 14-connected [Cu9(μ3-OH)4(μ2-OH)2]
enneanuclear copper(II) clusters, respectively. The blue sticks represent the 2-
connected double bte ligands.
The magnetic orbitals located on the CuII ions are only
favorably oriented to yield a considerable overlap on the mag-
netic orbitals of bridging atoms to transfer magnetic interac-
tions in many polynuclear Cu(II) complexes. Hatfield and
Hodgson proposed an empirical magnetostructural correla-
tion: the Cu–OH–Cu pathway with a Cu–OH–Cu bond angle
>97.6° mostly transfers antiferromagnetic interactions (J < 0),
with an increasing antiferromagnetic interaction as the
Cu–OH–Cu angle increases.20 Therefore, the magnetic exchange
interactions between the CuII centers can be considered by the
Cu–O–Cu bond angles. The Cu3 and Cu4 atoms may have a
ferromagnetic interaction due to the small bond angles of
Cu3–O16–Cu4 = 95.016(7)° and Cu3–O17–Cu4 = 93.926(7)°. The
magnetic exchanges between the other Cu(II) atoms should
have antiferromagnetic interactions because the Cu–OH–Cu
bond angles are >97.6°. An attempt to fit the magnetic
exchange using a theoretical model was unsuccessful due to
the complicated magnetic exchange pathways.
Magnetic properties
A preliminary magnetic study of compound 1 has been
performed. Magnetic susceptibilities were measured in the
1.8–300 K range with a SQUID magnetometer and are plotted
in Fig. 8. The magnetic moment μeff/molecule for the CuII
9
core in 1 is 4.368 μB (χMT = 2.385 cm−3 K mol−1) at 300 K, is
smaller than the expected value of μeff = 5.19 μB (χMT =
3.375 cm−3 K mol−1) for nine uncoupled S = 1/2 spins, indicat-
ing the presence of antiferromagnetic coupling. The value is
stable in the temperature range of 300 to 90 K and the value
is 4.370 μB (χMT = 2.387 cm−3 K mol−1) at 90 K. The value
decreases with decreasing the temperature and reaches
1.680 μB (χMT = 0.353 cm−3 K mol−1) at 1.8 K, which corresponds
to 1.732 μB (χMT = 0.375 cm−3 K mol−1) for one S = 1/2 spin. The
Curie–Weiss constants of C and θ are calculated to be
2.596 cm3 K mol−1 and −17.2 K respectively based on the χM
vs. T plot above 60 K (Fig. 9). The negative Weiss constant of
θ = −17.2 K indicates antiferromagnetic coupling between
the Cu(II) ions.
EPR spectra
The X-band EPR spectrum of compound 1 was recorded on a
polycrystalline powder sample at room temperature (Fig. S6
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in the ESI†). The EPR spectrum at room temperature shows a
broad band centered at g = 2.11.
In order to investigate the toxicity of the degradation prod-
uct after the photocatalysis experiment, the mixed-germs-
plate method was used to determine the antibacterial activity
of the substance using the Oxford plate assay system (in the
ESI†).22 The Staphylococcus aureus and Escherichia coli strains
were used as the indicating microorganisms. No inhibition
zone was found in the antibacterial activity experiment,
which shows that the degradation product after the photo-
catalysis experiment should be non toxic for the Staphylococcus
aureus and Escherichia coli strains.
Photocatalytic decomposition reactions
To study the photocatalytic activity of compound 1 in detail,
we selected methyl orange (MO) as a model dye contaminant
to evaluate the photocatalytic effectiveness in the purification
of wastewater. In the photocatalytic degradation process, the
organic dye is damaged and broken down into non hazard-
ous CO2 in water.11–13 The degradation experiment of methyl
orange (MO) was tracked by visible spectroscopy and the
results are depicted in Fig. 10. It was found that the degrada-
tion rate of MO is up to 76.1% at 280 min in the presence of
1. However, when the research was conducted in the blank
experiment in the absence of 1, the degradation efficiency of
the reaction was 7.4% in 280 min. Clearly, 1 is an effective
catalyst for the degradation of MO.
The photocatalytic reaction mechanism is complicated
and not very clear. During the photocatalytic process of
MOFs, UV-vis light may induce the MOFs/organic ligands (L)
to produce oxygen and/or nitrogen–metal charge transfer by
promoting an electron from the highest occupied molecular
orbital (HOMO) to the lowest unoccupied molecular orbital
(LUMO). The charge transfer excited state (MOFs/or L*) can
be deactivated by oxidizing the contaminant directly and/or
oxygenating water molecules into ˙OH radicals to complete
the photocatalytic process.11–13,21
After the photocatalytic degradation of the MO solution,
the photocatalyst (compound 1) can be separated by simple
centrifugation as it is undissolved in water. After
photocatalysis, the PXRD pattern of 1 is in good agreement
with that of the original compound, implying that 1 main-
tains its structural integrity after the photocatalysis reaction,
which confirmed that its stability towards photocatalysis is
good (Fig. S7 in the ESI†). A TOC (Total Organic Carbon)
measurement of the degradation product after the photo-
catalysis experiment gave a value of 1.724 mg L−1. The result
reveals that the TOC decreases obviously, which infers that
the dyes should degrade into carbon dioxide.
Conclusion
In summary, we hydrothermally synthesized a (3,14)-connected
three-dimensional MOF {[Cu9(OH)6(bte)2(sip)4(H2O)3]·6H2O}n
(1) based on the unprecedented enneanuclear copper(II) cluster
[Cu9(μ3-OH)4(μ2-OH)2]. 1 shows dominant antiferromagnetic
coupling interactions and good photocatalytic activity for the
degradation of methyl orange. This work provides new infor-
mation regarding polynuclear copper(II) chemistry. The design
and synthesis of new polynuclear copper(II) complexes is
underway in our laboratory.
Acknowledgements
This work was supported by the Natural Science Foundation
of China (No. 21171126), the Priority Academic Program
Development of Jiangsu Higher Education Institutions and
the Funds of Key Laboratory of Organic Synthesis of Jiangsu
Province. We thank Professor Davide M. Proserpio for the
topological analysis of the structure of 1.
References
1 (a) S. S. Han and W. A. Goddard III, J. Am. Chem. Soc.,
2007, 129, 8422; (b) L. J. Murray, M. Dinca and J. R. Long,
Chem. Soc. Rev., 2009, 38, 1294; (c) J. An, S. J. Geib and
N. L. Rosi, J. Am. Chem. Soc., 2010, 132, 38; (d) L. L. Wen,
J. B. Zhao, K. L. Lv, Y. H. Wu, K. J. Deng, X. K. Leng and
D. F. Li, Cryst. Growth Des., 2012, 12, 1603; (e) Z. Z. Lu,
R. Zhang, Y. Z. Li, Z. J. Guo and H. G. Zheng, J. Am.
Chem. Soc., 2011, 133, 4172; (f) A. Laguna, T. Lasanta,
J. M. Lopez-de-Luzuriaga, M. Monge, P. Naumov and
M. E. Olmos, J. Am. Chem. Soc., 2010, 132, 456; (g) C. S. Liu,
X. G. Yang, M. Hu, M. Du and S. M. Fang, Chem. Commun.,
2012, 48, 7459; (h) P. Yang, X. He, M. X. Li, Q. Ye, J. Z. Ge,
Z. X. Wang, S. R. Zhu, M. Shao and H. L. Cai, J. Mater.
Chem., 2012, 22, 2398; (i) K. A. Stevenson, C. F. C. Melan,
O. Fleischel, R. Wang and A. Petitjean, Cryst. Growth Des.,
2012, 12, 5169; (j) D. K. Cao, M. J. Liu, J. Huang, S. S. Bao
and L. M. Zheng, Inorg. Chem., 2011, 50, 2278.
2 (a) B. F. Hoskins, R. Robson and D. A. Slizys, J. Am. Chem.
Soc., 1997, 119, 2952; (b) B. F. Hoskins, R. Robson and
D. A. Slizys, Angew. Chem., Int. Ed. Engl., 1997, 36, 2336; (c)
J. Z. Gao, J. Yang, Y. Y. Liu and J. F. Ma, CrystEngComm,
Fig. 10 Photocatalytic degradation of
a MO solution under UV light using
compound 1; the black curve is the blank experiment without any catalyst.
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2012, 14, 8173; (d) X. L. Sun, Z. J. Wang, S. Q. Zang,
W. C. Song and C. X. Du, Cryst. Growth Des., 2012, 12, 4431.
3 (a) G. Aromí, L. A. Barrios, O. Roubeau and P. Gamez,
Coord. Chem. Rev., 2011, 255, 485; (b) J. P. Zhang and
X. M. Chen, Chem. Commun., 2006, 1689; (c) Y. Garcia,
C. Bravic, C. Gieck, D. Chasseau, W. Tremel and P. Gutlich,
Inorg. Chem., 2005, 44, 9723; (d) X. Zhu, Y. F. Feng, M. Li,
B. L. Li and Y. Zhang, CrystEngComm, 2012, 14, 79; (e)
N. Wang, J. G. Ma, W. Shi and P. Cheng, CrystEngComm,
2012, 14, 5198; (f) J. Zhao, D. S. Li, X. J. Ke, B. Liu, K. Zou
and H. M. Hu, Dalton Trans., 2012, 41, 2560.
4 (a) A. Messerschmidt, A. Rossi, R. Ladenstein, R. Huber,
M. Bolognesi, G. Gatti, A. Marchesini, R. Petruzzelli and
A. Finazzi-Agro, J. Mol. Biol., 1989, 206, 513; (b) O. Kahn,
Angew. Chem., Int. Ed. Engl., 1985, 24, 834; (c) D. E. Fenton
and H. Okawa, J. Chem. Soc., Dalton Trans., 1993, 1349; (d)
E. I. Solomon, U. M. Sundaram and T. E. Machonkin,
Chem. Rev., 1996, 96, 2563.
5 (a) See a thematic (Biomimetic Inorganic Chemistry) issue of
Chem. Rev., 2004, 104, pp. 347–1200; (b) J. Yoon,
L. M. Mirica, T. D. P. Stack and E. I. Solomon, J. Am. Chem.
Soc., 2005, 127, 13680; (c) S. I. Chan, V. C. C. Wang,
J. C. H. Lai, S. S. F. Yu, P. P. Y. Chen, K. H. C. Chen,
C. L. Chen and M. K. Chan, Angew. Chem., 2007, 119, 2038.
6 (a) R. J. Butcher, C. J. O'Connor and E. Sinn, Inorg. Chem.,
1981, 20, 537; (b) F. B. Hulsbergen, R. W. M. T. Hoedt,
G. C. Verschoor, J. Reedijk and A. Spek, J. Chem. Soc., Dalton
Trans., 1983, 539; (c) J. Comamond, B. Dietrich, J. M. Lehn
and R. Louis, J. Chem. Soc., Chem. Commun., 1985, 74; (d)
J. P. Costes, F. Dahan and J. P. Laurent, Inorg. Chem.,
1986, 25, 413; (e) M. Anagaroni, G. A. Ardizzoia,
T. Beringhelli, G. L. Monica, D. Gatteschi, N. Masclochi and
M. Moret, J. Chem. Soc., Dalton Trans., 1990, 3305; (f)
Y. Agnus, R. Louis, B. Metz, C. Boudon, J. P. Gisselbrecht
and M. Gross, Inorg. Chem., 1991, 30, 3155.
7 (a) M. S. Ray, S. Chattopadhyay, M. G. B. Drew, A. Figuerola,
J. Ribas, C. Diaz and A. Ghosh, Eur. J. Inorg. Chem.,
2005, 4562; (b) Q. G. Zhai, C. Z. Lu, S. M. Chen, X. J. Xu and
W. B. Yang, Cryst. Growth Des., 2006, 6, 1393; (c) B. Ding,
L. Yi, P. Cheng, D. Z. Liao and S. P. Yan, Inorg. Chem.,
2006, 45, 5799; (d) B. Sarkar, M. S. Ray, Y. Z. Li, Y. Song,
A. Figuerola, E. Ruiz, J. Cirera, J. Cano and A. Ghost,
Chem.–Eur. J., 2007, 13, 9297; (e) C. D. Nicola, F. Garau,
Y. Y. Karabach, L. M. D. R. S. Martins, M. Monari,
L. Pandolfo, C. Pettinari and A. J. L. Pombeiro, Eur. J. Inorg.
Chem., 2009, 666.
R. M. Cheng, Y. Song, Y. Z. Li, X. T. Chen, Z. L. Xue and
X. Z. You, Inorg. Chem., 2005, 44, 8011.
9 (a) E. Gojon, J. Gaillard, J. M. Latour and J. Laugier,
Inorg. Chem., 1987, 26, 2046; (b) S. Meenakumari and
A. R. Chakravarty, J. Chem. Soc., Dalton Trans., 1992, 2305;
(c) S. Meenakumari, M. Lakshminarayanan, S. K. Tiwary and
A. R. Chakravarty, Inorg. Chem., 1995, 34, 5091; (d)
G. S. Papaefstathiou, C. P. Raptopoulou, A. Tsohos, A. Terzis,
E. G. Bakalbassis and S. P. Perlepes, Inorg. Chem., 2000, 39,
4658; (e) S. Nellutla, J. van Tol, N. S. Dalal, L. H. Bi, U. Kortz,
B. Keita, L. Nadjo, G. A. Khitrov and A. G. Marshall,
Inorg. Chem., 2005, 44, 9795.
10 (a) S. Khanra, T. Weyhermuller and P. Chaudhuri, Dalton
Trans., 2009, 3847; (b) M. S. E. Fallah, A. Escuer, R. Vicente,
F. Badyine, X. Solans and M. Font-Bardia, Inorg. Chem.,
2004, 43, 7218; (c) X. Ottenwaelder, J. Cano, Y. Journaux,
E. Rivire, C. Brennan, M. Nierlich and R. Ruiz-Garcia, Angew.
Chem., Int. Ed., 2004, 43, 850; (d) V. A. Milway, V. Niel,
T. S. M. Abedin, Z. Xu, L. K. Thompson, H. Grove,
D. O. Miller and S. R. Parsons, Inorg. Chem., 2004, 43, 1874;
(e) P. Mialane, A. Dolbecq, J. Marrot, E. Rivire and
F. Secheresse, Chem.–Eur. J., 2005, 11, 1771.
11 (a) F. Wang, Z. S. Liu, H. Yang, Y. X. Tan and J. Zhang,
Angew. Chem., Int. Ed., 2011, 50, 450; (b) G. H. Cui, C. H. He,
C. H. Jiao, J. C. Geng and V. A. Blatov, CrystEngComm,
2012, 14, 4210; (c) H. X. Yang, T. F. Liu, M. N. Cao, H. F. Li,
S. Y. Gao and R. Cao, Chem. Commun., 2010, 46, 2429.
12 (a) M. C. Das, H. Xu, Z. Y. Wang, G. Srinivas, W. Zhou,
Y. F. Yue, V. N. Nesterov, G. D. Qian and B. L. Chen, Chem.
Commun., 2011, 47, 11715; (b) T. Wen, D. X. Zhang and
J. Zhang, Inorg. Chem., 2013, 52, 12; (c) J. Lu, J. X. Lin,
X. L. Zhao and R. Cao, Chem. Commun., 2012, 48, 669.
13 (a) Y. Q. Chen, G. R. Li, Y. K. Qu, Y. H. Zhang, K. H. He,
Q. Gao and X. H. Bu, Cryst. Growth Des., 2013, 13, 901; (b)
Y. Gong, T. Wu and J. H. Lin, CrystEngComm, 2012, 14, 3727;
(c) J. X. Meng, Y. G. Li, H. Fu, X. L. Wang and E. B. Wang,
CrystEngComm, 2011, 13, 649.
14 (a) X. Zhu, J. W. Zhao, B. L. Li, Y. Song, Y. M. Zhang and
Y. Zhang, Inorg. Chem., 2010, 49, 1266; (b) X. Y. Wang,
B. L. Li, X. Zhu and S. Gao, Eur. J. Inorg. Chem., 2005, 3277.
15 (a) M. Li, Q. Ling, Z. Yang, B. L. Li and H. Y. Li, CrystEngComm,
2013, 15, 3630; (b) X. Zhu, Q. Chen, Z. Yang, B. L. Li and
H. Y. Li, CrystEngComm, 2013, 15, 471; (c) M. Li, S. Zhao,
Y. F. Peng, B. L. Li and H. Y. Li, Dalton Trans., 2013, 42, 9771;
(d) J. Wang, X. Zhu, Y. F. Cui, B. L. Li and H. Y. Li,
CrystEngComm, 2011, 13, 3342; (e) X. Zhu, X. G. Liu, B. L. Li and
Y. Zhang, CrystEngComm, 2009, 11, 997; (f) L. Y. Wang, Y. Yang,
K. Liu, B. L. Li and Y. Zhang, Cryst. Growth Des., 2008, 8, 3902;
(g) X. G. Liu, L. Y. Wang, X. Zhu, B. L. Li and Y. Zhang, Cryst.
Growth Des., 2009, 9, 3997; (h) X. Zhu, P. P. Sun, J. G. Ding,
L. B. Li and H. Y. Li, Cryst. Growth Des., 2012, 12, 3992.
8 (a) G. A. Senchyk, A. B. Lysenko, H. Krautscheid,
E. B. Rusanov, A. N. Chernega, K. W. Krämer, S. X. Liu,
S. Decurtins and K. V. Domasevitch, Inorg. Chem., 2013, 52,
863; (b) E. C. Yang, Z. Y. Liu, X. J. Shi, Q. Q. Liang and
X. J. Zhao, Inorg. Chem., 2010, 49, 7969; (c) E. C. Yang,
Y. L. Yang, Z. Y. Liu, K. S. Liu, X. Y. Wu and X. J. Zhao,
CrystEngComm, 2011, 13, 2667; (d) E. C. Yang, B. Ding,
Z. Y. Liu, Y. L. Yang and X. J. Zhao, Cryst. Growth Des.,
2012, 12, 1185; (e) H. A. Habib, J. Sanchiz and C. Janiak,
Inorg. Chim. Acta, 2009, 362, 2452; (f) J. H. Zhao,
16 G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr.,
2008, 64, 112.
17 Crystal data for compound 1: C44H52Cu9N12O43S4, Mr
=
2137.08, monoclinic, space group P21/n, a = 11.4086(15), b =
25.257(3), c = 12.6476(17) Å, β = 103.292(3)°, V = 3546.7(8) Å3,
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Paper
Z = 2, Dc = 2.001 g cm−3, F(000) = 2138, μ = 2.871 mm−1
CrystEngComm
,
20 (a) V. H. Crawford, H. W. Richardson, J. R. Wasson,
D. J. Hodgson and W. E. Hetefield, Inorg. Chem., 1976, 15,
2107; (b) E. Dixon-Estes, W. E. Estes, R. P. N. Scaringe,
W. E. Hatfield and D. J. Hodgson, Inorg. Chem., 1975, 14,
2564; (c) E. Ruiz, P. Alemany, S. Alvarez and J. Cano,
Inorg. Chem., 1997, 36, 3683.
21 J. Guo, J. Yang, Y. Y. Liu and J. F. Ma, CrystEngComm,
2012, 14, 6609.
22 Z. Song, Q. Liu, H. Guo, R. Ju, Y. Zhao, J. Li and X. Liu,
Bioresour. Technol., 2012, 111, 504.
18076 reflections measured, 6922 (Rint = 0.0464) unique
reflections, 539 parameters, R1 = 0.0743, wR2 = 0.1752, S =
1.076. CCDC: 928643.
18 W. Liu and H. H. Thorp, Inorg. Chem., 1993, 32, 4102.
19 (a) V. A. Blatov, M. O'Keeffe and D. M. Proserpio,
CrystEngComm, 2010, 12, 44; (b) E. V. Alexandrov, V. A. Blatov,
A. V. Kochetkova and D. M. Proserpio, CrystEngComm,
2011, 13, 3947; (c) M. O'Keeffe and O. M. Yaghi, Chem. Rev.,
2012, 112, 675; (d) http://www.topos.samsu.ru/download.html.
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