A {Co9IICo3III} dodecanuclear cluster based on o-vanillin oxime: Synthesis, structures and properties

Article abstract of DOI:10.1016/j.poly.2016.03.034

A new dodecanuclear cluster [Co₉^IICo₃^III(MeOsalox)₆(OAc)₁₅(H₂O)₆]·2MeCN·2H₂O (1) (H₂MeOsalox = 3-methyloxysalicylaldoxime) was synthesized under

Full text of DOI:10.1016/j.poly.2016.03.034

Accepted Manuscript
II
III
A {Co Co 3} dodecanuclear cluster based on o-vanillin oxime: synthesis,
9
structures and properties
Yu Li, Yaru Qin, Yong Wang, Wei Liu, Yahong Li
PII:
S0277-5387(16)30024-9
DOI:
http://dx.doi.org/10.1016/j.poly.2016.03.034
POLY 11899
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
30 January 2016
8 March 2016
II
III
Please cite this article as: Y. Li, Y. Qin, Y. Wang, W. Liu, Y. Li, A {Co Co 3} dodecanuclear cluster based on
9
o-vanillin oxime: synthesis, structures and properties, Polyhedron (2016), doi: http://dx.doi.org/10.1016/j.poly.
2
016.03.034
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II
III
A {Co Co } dodecanuclear cluster based on o-vanillin
9
3
oxime: synthesis, structures and properties
*
*
Yu Li, Yaru Qin, Yong Wang, Wei Liu, Yahong Li
College of Chemistry, Chemical Engineering and Materials Science, Soochow
University, Suzhou 215123, China.
Abstract:
II
III
A new dodecanuclear cluster [Co
9
Co
3
(MeOsalox)
6
(OAc)15(H
2
O)
6
]·2MeCN·2H
2
O
(
1) (H MeOsalox = 3-methyloxysalicylaldoxime) was synthesized under solvothermal
2
conditions and characterized by IR, elemental analyses (EA), single-crystal X-ray
diffraction and powder XRD. Magnetic investigations reveal that complex 1 exhibits
antiferromagnetic interactions between the cobalt centers.
Keywords: Cobalt; Aldoxime; Polynuclear complex; Crystal structure; Magnetic
properties
1. Introduction
The fabrication of nanoscale metal clusters exhibiting quantum size effects and
unusual chemical reactivity has attracted widespread attention, not only due to their
multifarious architectures, but also because of their fascinating potential applications
in metalloenzyme models, molecular magnets, nanoscale catalysts, as well as
nanophotonic and nanoelectronic devices [1]. In order to deeply understand the
fundamental aspects dominating the chemical properties of polynuclear nanoclusters,
great effort has been devoted to 3d transition-metal complexes, especially those with
high-spin (S) ground-state values together with a strong uniaxial anisotropy and
single-molecule-magnetic (SMM) behavior [2,3]. Cobalt nanoclusters draw particular
interest due to their flexible structures and magnetic properties [4]. A library of cobalt
*
To whom correspondence should be addressed. Email: weiliu@suda.edu.cn (W. Liu),
liyahong@suda.edu.cn (Y. H. Li).
1

7 8
clusters, e.g. Co [5], Co [6], Co10 [7], Co12 [8,9], Co13 [5a,5g,8], Co16 [10], Co19 [6,7],
Co20 [11], Co24 [12], Co32 [13] and Co36 [14], have been reported to date.
Nevertheless, compared with manganese and iron [15], the number of cobalt-based
clusters with a high-nuclearity is relatively small.
One significant factor in the creation of novel coordination clusters is the choice
of primary ligand, which dictates the molecular topology and intramolecular magnetic
exchange between the paramagnetic metal ions. The employment of N, O containing
ligands with multiple coordination sites, such as Schiff base ligands [16], has been
probed as an efficient synthetic protocol. As analogues of Schiff base ligands,
aldoximes are important chelating ligands ubiquitous in coordination and analytical
chemistry, as well as in the biological field, over the past two decades [17]. Diverse
types of aldoximes, including pyrrole aldoximes [18], pyridine aldoximes [19],
imidazole aldoximes [20] and salicylaldoximes [21], reveal their powerful
coordination propensity and ability to form various polynuclear systems. We have
also reported the employment of 2-pyridinealdoxime for the construction of
II
II
wheel-like Mn
6 6
and Ni clusters previously [22]. Among the expanding series of
multidentate aldoximes, the 3-substituted salicylaldoximes, derived from the
corresponding aldehydes [23], can be doubly deprotonated when bound to metal ions,
and provide versatile chelating and bridging patterns. However, the utilization of such
a type of ligands has previously generated only a small number of complexes, i.e.
mononuclear V [24a,b], Ni [24c], Cu [24d] and Co [24e], and multinuclear Dy
3
, Tb
[25b] and Co13 [5a,8b]. It is anticipated that the exploitation of
-substituted salicylaldoximes would give more high-nuclearity clusters with
properties. In the present work we have selected
-methyloxysalicylaldoxime (H MeOsalox, o-vanillin oxime) in combination with
solvothermal techniques for the synthesis of a unique crown-like dodecanuclear
3
[
25a], Co
4
3
intriguing
3
2
II
III
{
9 3
Co Co } cluster.
2. Experimental
2

2
.1. Materials and instruments.
The ligand 3-methyloxysalicylaldoxime (H
2
MeOsalox) was prepared by
coupling -vanillin with hydroxylamine hydrochloride in methanol by a
o
procedure reported elsewhere [25]. The reagents and solvents were
commercially available and used as received without further purification. All
manipulations were performed under aerobic and solvothermal conditions using
reagents and solvents as received. The C, H and N microanalyses were carried
out with a Carlo-Erba EA1110 CHNO-S elemental analyzer. FT-IR spectra
-
1
were recorded in the range 400-4000 cm on a Bruker VERTEX 70
spectrometer. Thermal gravimetric analysis (TGA) was conducted on a TA SDT
-
1
2
Q600 instrument in flowing N with a heating rate of 5 °C min . Powder X-ray
diffraction (PXRD) was recorded on a Rigaku D/Max-2500 diffractometer at 40
kV and 100 Ma with a Cu-target tube and a graphite monochromator.
Variable-temperature dc magnetic susceptibility data were collected using a
Quantum Design MPMS-7 SQUID magnetometer. Diamagnetic corrections
were applied to the observed paramagnetic susceptibilities using Pascal’s
constants.
II
III
2
9 3 6 2 6 2
.2. Synthesis of [Co Co (MeOsalox) (OAc)15(H O) ]·2MeCN·2H O (1).
2 2 2
A mixture of Co(OAc) ·4H O (0.025 g, 0.1 mmol), H MeOsalox (0.017 g, 0.1
mmol), acetonitrile (0.5 mL) and MeOH (0.5 mL) was placed in a Pyrex tube
which was heated at 60 °C for 3 days and then cooled to room temperature to
give dark brown crystals of the product. The crystals were collected by
filtration, washed with acetonitrile and dried in air. Yield: 23 %. Anal. Calc. (%)
for
84 9 64
C H128Co12N O
II
III
{
[Co
9 3 6 2 6 2
Co (MeOsalox) (OAc)15(H O) ]·3MeCN·10H O}: C, 33.68; H, 4.30;
-
1
N, 4.20. Found (%): C, 33.23; H, 4.25; N, 4.71. Selected IR data (cm ): 1583
(s), 1415 (s), 1244 (s), 1096 (m), 970 (m), 728 (m), 665 (m).
3

2
.3. X-ray diffraction determination.
Data were collected for complex
1at room temperature on a Bruker Smart
II
Apex diffractometer with the
ω
and
φ
scan technique. The structure was
2
solved by direct methods using SHELXS-97 [26] and refined on
F
using
full-matrix least-squares with SHELXL-97 [27]. All non-hydrogen atoms were
refined anisotropically. The crystal data and structure refinements of complex
1
are listed in Table S1. Selected bond lengths and bond angles of the complex
are listed in Table 1.
3. Results and discussions
3
.1. Syntheses and powder X-ray diffraction.
The facile reaction of Co(OAc)
2 2 2
·4H O and H MeOsalox in a 1:1 ratio under
solvothermal conditions afforded a dodecametallic cluster with the formula
II
III
[
9 3 6 2 6 2
Co Co (MeOsalox) (OAc)15(H O) ]·2MeCN·2H O. Through the simple
and efficient solvothermal techniques [28], a novel coordination complex,
which was not accessible by “conventional” trials such as evaporation and
diffusion, was achieved. No crystal was given without the participation of
acetonitrile in the reaction, indicating that the solvent plays a vital role in the
formation of complex
The experimental powder XRD patterns for a microcrystalline sample of
are consistent with the simulated diffraction patterns generated using the
1.
1
respective single-crystal X-ray data of
pure (Fig. S1).
1, indicating that the samples are phase
3
.2. FT-IR spectra and thermogravimetric analysis.
-
1
A broad band in the FT-IR spectrum at around 3450 cm indicates the presence
-
1
2
of solvate H O molecules (Fig. S2). The strong bands at 1583 and 1415 cm
are attributed to the respective
ν
as(COO) and
s
ν (COO) vibrations of
-
-1
CH
3
COO [19,29]. The band at 1096 cm with medium intensity may be
4

assigned to the
For a microcrystalline sample of complex
TGA) were performed under a N atmosphere from room temperature to
000 °C (Fig. S3). The weight loss of 10.10 % in the first stage from room
temperature to 200 °C corresponds to the loss of three solvate acetonitrile
molecules and ten solvate H O molecules, (calculated value 10.13 %); the
molecular structure starts to decompose when the temperature reaches 200 °C.
The remaining residue corresponds to 3/2 Co molecules and 9 CoO
molecules, total weight 29.74 % (calculated value 30.82 %).
ν(NO) oximate mode [30].
1
, thermogravimetric analyses
(
2
1
2
2
O
3
3
.3. Description of the crystal structure.
Complex
1 crystallizes in the non-centrosymmetric trigonal space group R3c,
and consists of one dodecanuclear cluster, two solvate acetonitrile and two
solvate water molecules. Each cluster lies on a crystallographic 3-axis, with six
molecules in the unit cell (hexagonal setting).
All twelve cobalt ions are connected by six deprotonated o-vanillin oxime
-
ligands, fifteen CH
3
COO anions, and six water molecules (Fig. 1a). Compared
with the first cobalt metallacrowns reported by the group of Escuer and
Perlepes in 2005 [31], the cyclic backbone of complex is best described as a
8-metallacrown-6 framework (Fig. 1b,c). The Co1 (Co1A, Co1B) and Co3
1
1
(
Co3A, Co3B) atoms are coplanar, while the Co2 (Co2A, Co2B) and Co4
Co4A, Co4B) atoms deviate from their mean plane (Fig. S4). Thus, the {Co12}
(
core is arranged in a novel motif with a “chair-hexagon” combination (Fig. 1d).
As estimated from the distance between two opposite cobalt ions, the diameter
of the crown is 9.4 Å. The two solvate CH
located outside of the crown.
3 2
CN and two H O molecules are
5

(
a)
(b)
(
c)
(d)
Fig. 1. (a) Partially labelled crystal structure of
metal-nitrogen core of , showing two different exchange interactions. (c) The
metallic skeleton of highlighting the 18-membered-6 metallacrown. (d) The
simplified metallic core in
blue. Hydrogen atoms are omitted for clarity.
1. (b) The metal-oxygen and
1
1
II
III
1
. Color scheme: Co , green; Co , purple; O, red; N,
Complex
1 joins the increasing cyclic transition-metal dodecanuclear {M12}
family [9,32-44], in which a few examples of {Co12} members,
[
[
[
Co12(chp)12(O
2
CMe)12(H
[Co(µ-OH)(µ-4-NO
(OH) (Ac) 2DMF (H
2
O)
6
(THF)
6
]
[9a],
PPN]
2
2
-pz)(µ-3,5-Me
2
-pz)]12[NO
2
]
2
·
H
2
O
·
xTHF [9b] and
II
Co 12(L)
6
6
6
]
·
2
L, a rhodamine 6G derivative) [9c], have
is quite distinct from those clusters in
been reported. Obviously, complex
structural topology.
1
Four crystallographically independent Co ions are included in the cluster.
Each Co ion is six-coordinate, and the detailed coordination environments are
listed in Table 1. The oxidation states of the cobalt ions were deduced from
bond-length and charge-balance considerations, and further confirmed by BVS
6

(
bond valence sum) calculations (for BVS calculation results, see Table S2)
45]. The Co1, Co2 and Co4 atoms have a distorted CoO octahedral geometry,
[
6
with Co-OMeOsalox/OAc distances in the range 2.000(6)-2.334(7) Å, indicating that
II
they are Co ions. The Co3 center is in a distorted CoN
2
O
4
environment, with
Co-NMeOsalox distances in the range 2.033(8)-2.045(7) Å and Co-OMeOsalox/OAc
III
distances in the range 1.911(6)-1.921(6) Å, suggesting it to be a Co ion. Thus,
II
III
complex
9 3
1 is a mixed-valence Co Co species.
2-
1
2
1
2
-
Fig. 2 Coordination modes of MeOsalox (η :η :η :η :µ
4
3
) and CH COO
1
1
(
η :η :µ ) anions in complex 1.
2
-
As depicted in Fig. 2, Co1 connects to Co2 via two CH
3
COO and one
single-atom Ooxime bridge, while Co1 connects to Co4 in the same fashion. Co3
-
is linked to Co2 through one CH
3
COO anion, one phenolate O atom and one
two-atom N-Ooxime bridge. Co3 is linked to Co4 through one phenolate O atom
and one two-atom N-Ooxime bridge. Co1 and Co3 are connected only by one
2-
two-atom N-Ooxime bridge. All the MeOsalox anions in the crystal are doubly
1
2
1
2
deprotonated, acting in novel η :η :η :η :µ
five-membered CoC ring and a six-membered CoC
deprotonated acetate anions adopt η :η :µ
from 3.3365(18) to 3.8476(22) Å, and the Co-O-Co angles are in the range
13.6(3)-123.4(3)° (Table S3), which are comparable to those of cyclic {Co12}
4
bridging fashions, generating a
NO ring. The
modes. The Co···Co distances range
2
O
2
3
1
1
2
1
clusters reported in the literature [9a-c]. No intermolecular interactions were
observed in the structure.
7

After comparing cluster
1 with other cobalt complexes containing a similar
ligand, i.e. mononuclear [24e], tetranuclear [25b] and butterfly-like
tridecanuclear [5a,8b] complexes, we found that the structures of the complexes
change by varying the anions of the metal salts, solvents and ancillary ligands
(Table S4). Moreover, the choice of reaction conditions (evaporation or
solvothermal method) is also important. The substituents at the 3-position of the
salicylaldoximes seem to have less effect on the nuclearity of the clusters [5a,8b]. In
-
our case, the small bridging acetate anions (CH
3
COO ), involved as auxiliaries
II
III
or a template, are essential for the preparation of the cyclic {Co
structure.
9 3
Co }
Table 1 Selected bond lengths (Å) and angles (°) for 1.
Bond
Distance
Bond
Distance Bond
Distance
2.208(6)
2.121(6)
2.006(6)
2.186(6)
1.921(6)
1.917(6)
2.067(6)
2.054(6)
2
-
2-
-
Co1-O3A (MeOsalox ) 2.288(6)
Co1-O6 (MeOsalox )
2.000(6)
2.170(6)
2.133(6)
2.066(6)
2.045(7)
2.177(5)
2.081(7)
2.334(7)
Co1-O7 (OAc )
-
-
-
Co1-O9 (OAc )
2.110(6)
2.065(6)
2.007(6)
2.033(8)
1.911(6)
2.234(7)
2.083(6)
Co1-O11 (OAc )
Co1-O16A(OAc )
2
-
2-
2-
Co2-O1 (MeOsalox )
Co2-O2 (MeOsalox )
Co2-O6 (MeOsalox )
-
-
-
Co2-O10 (OAc )
Co2-O12 (OAc )
Co2-O13 (OAc )
2
-
2-
2-
Co3-N1 (MeOsalox )
Co3-N2 (MeOsalox )
Co3-O1 (MeOsalox )
2
-
-
Co3-O4 (MeOsalox )
Co3-O1W (H
2
O)
Co3-O14 (OAc )
2
-
2-
Co4-O2W (H O)
2
Co4-O3 (MeOsalox )
Co4-O4 (MeOsalox )
2
-
-
-
Co4-O5 (MeOsalox )
Angle
Co4-O8B (OAc )
Co4-O15 (OAc )
Angle
Angle
O6-Co1-O3A
O6-Co2-O2
175.5(2)
162.2(3)
170.7(3)
173.8(2)
O9-Co1-O7
O10-Co2-O1
O4-Co3-O1
O3-Co4-O5
175.4(2)
170.6(3)
177.6(2)
172.2(3)
O16A-Co1-O11
O12-Co2-O13
O14-Co3-O1W
O15-Co4-O4
163.1(2)
170.4(2)
161.6(3)
170.1(3)
N1-Co3-N2
O2W-Co4-O8B
Symmetry transformations used to generate the equivalent atoms: #A -x+y, 1-x, z; #B -y+1, x-y+1,
z.
3
.4. Magnetic properties
Variable-temperature dc magnetic susceptibility data were collected on
powdered microcrystalline samples of complex
1
in the 300-2.0 K range under
at 300 K is 29.1
an applied field of 1 kOe (Fig. 3). The T value of complex 1
χ
M
3
−1
3
-1
cm mol K, which is larger than the expected value of 25.875 cm mol K for
8

II
III
nine Co (
orbital contributions of the distorted octahedral Co ions.
temperature is lowered, the value decreases gradually to a minimum of
1.46 cm mol K at 2 K. This behavior indicates that the exchange between
S = 3/2) and three Co (S = 2) uncoupled spins, possibly due to the
II
3,5-12
As the
M
χ T
3
-1
1
the metal ions is antiferromagnetic in nature. The reciprocal magnetic
susceptibilities in the temperature range 50-300 K follow the Curie-Weiss Law
3
-1
of 1/
χ
M
= (T - θ C with the Curie constant C = 31.80 cm mol K and Weiss
)/
constant
θ
= -27.08 K, which confirms the existence of antiferromagnetic
II
III
9 3
interactions between the metal centers in the {Co Co } cluster.
Fig. 3. Temperature dependence
dependence of the magnetic susceptibilities in the form of
kOe. The red solid line corresponds to the best fit from 300 to 50 K.
M M
χ T and χ for 1 at 1 kOe. Inset: temperature
−
1
χ
M
vs. T for
1
at 1
4. Conclusions
In summary, a new mixed-valence cobalt(II/III) dodecanuclear cluster
1
was
prepared based on
o-vanillin oxime (3-methyloxysalicylaldoxime). Cluster 1
represents an elegant example of using a solvothermal synthesis to isolate a
high-nuclearity cluster. Moreover, the results demonstrate the coordinative
9

2
flexibility and versatility of the multidentate ligand H MeOsalox for
constructing complexes with interesting properties. It is envisioned that our
findings will provide new impetus for the development of new strategies for
preparing new high-nuclearity clusters. Further studies on the binding of such a
type of ligand to various metal ions are now in progress.
Appendix A. Supplementary data
CCDC 1058964 contains the supplementary crystallographic data for complex 1.
These
data
can
be
obtained
free
or
of
from
charge
via
http://www.ccdc.cam.ac.uk/conts/retrieving.html,
the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44)
1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be found, in the online
version.
Acknowledgements
This project was supported by the Natural Science Foundation of China
(21272167 and 21201127), Scientific Research Foundation of Soochow
University (SDY2012A07) and is a project funded by the Priority Academic
Program Development of Jiangsu Higher Education Institutions (PAPD).
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Graphical Abstract:
II
III
A {Co Co } dodecanuclear cluster based on o-vanillin oxime:
9
3
synthesis, structures and properties
Yu Li, Yaru Qin, Yong Wang, Wei Liu,* Yahong Li*
One mixed-valence cobalt(II/III) dodecanuclear cluster bridged by doubly
deprotonated O-vanillin oxime and acetate anions has been assembled.
Antiferromagnetic interactions between the cobalt ions are observed.
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