Two 2-D multifunctional cobalt(ii) compounds: field-induced single-ion magnetism and catalytic oxidation of benzylic C-H bonds

Article abstract of DOI:10.1039/C6DT04551K

Two cobalt(ii) compounds, namely, {[Co(HL)(bpy)(H₂O)₂]·DMF}_n (1), and {[Co(HL)(bpe)]·0.5bpe}_n (2) (H₃L = 1,3-bis(2-carboxylphenoxy)benzoic acid, bpy = 4,4′-bipyridine, bpe = 4,4′-vinylenedipyridine), have been synthesized using cobalt(ii) transition metal salt with phenolic carboxylic acid and different N-donor ligands. The compounds were fully characterized by elemental analysis, infrared spectroscopy (IR), single crystal X-ray diffraction analysis, and thermogravimetric analysis (TGA). Both compounds exhibit 2-D (4,4)-sql networks but with a wavelike and a double layered arrangement, respectively. Remarkably, these two compounds not only exhibit field-induced single-ion relaxation magnetization but also exceptional catalytic activities of benzylic C-H oxidation (conv. 90.3-99%; sele. 98.1-99%).

Full text of DOI:10.1039/C6DT04551K

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Two 2ꢀD multifunctional cobalt(II) compounds:
Fieldꢀinduced singleꢀion magnetism and catalytic oxidation
of benzylic CꢀH bonds
a
a
b
a
a
a
Ranran Ma , Zhiwei Chen , Fan Cao , Suna Wang *, Xianqiang Huang *, Yunwu Li ,
a
a
a
Jing Lu , Dacheng Li , Jianmin Dou *
[
a] Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell
Technology, School of Chemistry and Chemical Engineering, Liaocheng University,
Liaocheng, 252059, P. R. China. Tel: +86ꢀ0635ꢀ8230669.
[
b]QingdaoUniversityofScience&Technology, College of Chemistry and Molecular
Engineering, 266042, P. R. China. Tel: +86ꢀ0532ꢀ84022681.
Email: wangsuna@lcu.edu.cn; hxq@lcu.edu.cn jmdou@lcu.edu.cn
;
Abstract.Two cobalt(II) compounds, namely, {[Co(HL)(bpy)(H
2 2 n
O) )]·DMF} (1),
and {[Co(HL)(bpe)]·0.5bpe} (2) (H L = 1,3ꢀbis(2ꢀcarboxylphenoxy)benzoic acid,
n
3
bpy = 4,4'ꢀbipyridine, bpe = 4,4'ꢀvinylenedipyridine), have been synthesized using
cobalt(II) transition metal salt with phenolic carboxylic acid and different Nꢀdonor
ligands. The compounds were fully characterized by elemental analysis, infrared
spectroscopy (IR), single crystal Xꢀray diffraction analysis, and thermogravimetric
analysis (TGA). Both compounds exhibit 2ꢀD (4,4)ꢀsql networks but with wavelike
and double layered arrangement, respectively. Remarkably, these two compounds not
only exhibit fieldꢀinduced singleꢀion relaxation magnetization but also exceptional
catalytic activities of benzylic CꢀH oxidation (Conv. 90.3ꢀ99%; Sele. 98.1ꢀ99%).
Introduction.
Recent years have witnessed the focus attention and rapid progress of
metalꢀorganic frameworks (MOFs). The potential applications of general MOFs, such
as gas adsorption, luminescence, fluorescent sensing, nonlinear optics, magnetism,
ferroelectric and catalysis, could be combined and integrated into individual
1
ꢀ4
frameworks, resulting multifunctional MOFs. Compared with MOFs with a single
property, these specific materials may find new application in more areas. How to
assemble the building blocks, including ‘functional’ metal centers and ‘functional’
organic bridging ligands, as well as their special arrangements, is very crucial to
construct these materials.
1

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As a new subclass of single molecule magnets (SMMs), singleꢀion magnets (SIMs)
with slow magnetic relaxation derived from a single paramagnetic ion, also attracted
5
the attention of chemists. Due to the absence of large groundꢀstate spin and strong
easyꢀaxis magnetic anisotropy, lanthanide metals are preferred to construct SIMs,
6
ꢀ7
8
especially Dy. Since the first 3d SIM was reported by Long et al , a few compounds
based on dꢀblock metals, including Mn, Ni, Fe, and Co, have also been reported to
9
ꢀ14
exhibit SIM properties. Remarkably, cobalt is a fine candidate for the construction
of SIMs on account of the strong spinꢀorbit coupling. A few cobalt examples,
including 0ꢀD molecules and highꢀdimensional frameworks with negligible metal
1
5ꢀ17
coupling interactions with large metal···metal separation,
special magnetization.
could exhibit such
Additionally, the oxidation of CꢀH bonds is one of the most important and
fundamental reactions. Highly efficient catalysis of CꢀH bonds remains a challenge
and great efforts had been made in exploring new catalysts. The oxidation of benzylic
CꢀH bonds, for instance, is a powerful tool to generate high value chemical feedstock
from less expensive raw materials such as alkyl aromatics. In this regard, the means to
convert benzylic hydrocarbons into valuable compounds have received considerable
attention in recent years. As of today, many excellent results using transition metal
18ꢀ20
materials as catalysts have been reported by some prominent chemists.
However, a
few MOFs have shown catalytic activity in the oxidation of benzylic CꢀH bonds with
unsatisfactory conversion rate and/or selectivity. Therefore, design of the
heterogeneous molecular catalysts containing catalytic active sites has proved to be
the most valuable strategy to solve this problem.
We have recently reported a series of multifunctional lanthanideꢀbased MOFs with
gas adsorption and fluorescent sensing/slow magnetism properties from functional
21
dicarboxylate ligands. Along with our investigation in this field, two cobalt
coordination compounds, {[Co(HL)(bpy)(H O) )]·DMF} (1), and
[Co(HL)(bpe)]·0.5bpe} (2) (H L = 1,3ꢀbis(2ꢀcarboxylphenoxy)benzoic acid, bpy =
,4'ꢀbipyridine, bpe = 4,4'ꢀvinylenedipyridine), were obtained from a flexible
2
2
n
{
4
n
3
etherꢀlinked multicarboxylate ligand. Both compounds could be considered as
multifunctional materials with both fieldꢀinduced singleꢀion relaxation magnetization
and excellent benzylic CꢀH oxidation catalytic activities.
Experimental
2

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Materials and methods
H L (1,3ꢀbis(2ꢀcarboxylphenoxy)benzoic acid) was purchased from Jinan Henghua
3
Sci. & Technol. Co. Ltd. Bpy (4,4'ꢀbipyridine) and bpe (4,4'ꢀvinylenedipyridine) were
purchased from SigmaꢀAldrich. Other reagents were commercially available and used
without further purification. The hydrothermal reactions were performed in 23 mL
stainless steel autoclaves lined with Teflon under autogenous pressure. The
emission/excitation spectra were recorded with a Hitachi 850 fluorescence
spectrophotometer. C, H and N analyses were carried out with a PerkinꢀElmer 240C
ꢀ1
elemental analyzer. The FTꢀIR spectra (4000ꢀ400 cm ) were recorded from KBr
pellets with a VECTOR 22 spectrometer. Powder Xꢀray diffraction (PXRD) data were
collected over the 2θ range of 5ꢀ50° using a Philips X'Pert diffractometer with Cu Kα
radiation (λ= 1.5418 Å) at room temperature. Thermal analyses were performed on a
TGA V5.1A Dupont 2100 instrument from room temperature to 800 °C with a heating
ꢀ1
rate of 20K·min under flowing nitrogen. The GC analyses were performed on
Shimadzu GCꢀ2014C with a FID detector equipped with an Rtxꢀ1701 Sil capillary
column. The GCꢀMS spectra were recorded on Agilent 7890Aꢀ5975C at an ionization
voltage of 1200 V. Atomic absorption analysis was measured by inductively coupled
plasma (ICP) on an ICPꢀ6000 analyzer.
Synthesis of {[Co(HL)(bpy)(H
A mixture of H L (0.0394g, 0.10 mmol), CoCl
0.0156g, 0.10 mmol) was dissolved in 12 mL solution of DMF/H
mixture was sealed in a Teflonꢀlined stainless steel vessel (25 mL) and heated at
0ºCunder autogenous pressure for 72 h, and then cooled to room temperature.
Colourless crystals were obtained, crystals were filtrated washed with water and dried
in air.Yield: 55% (based onH = 716.55): calcd. C 56.99, H
2 2 n
O) )]·DMF} (1)
3
2
(0.0130g, 0.10 mmol) and bpy
O (1:1, v/v). The
(
2
8
3
31 3 r
L). C34H N O11Co (M
ꢀ
1
4
1
6
.36, N 5.86%; found C 56.92, H 4.32, N 5.79%. IR (KBr pellet: cm ):3414(s),
655(m), 1606(s), 1589(s), 1440(vs), 1213(m), 1133(w), 1096(w), 821(w), 767(w),
32(w), 496(w).
n
Synthesis of {[Co(HL)(bpe)]·0.5bpe} (2)
The procedure was the same as that of 1 except that bpy was replaced by bpe
0.0182 g, 0.10 mmol). Claret blockscrystalsof 2 were obtained, filtrated, washed with
(
water and dried in air.Yield: 54% (based onH
3 27 3 8 r
L).C39H N O Co (M = 724.57):calcd.
ꢀ1
C 64.65, H 3.76, N 5.80%; found C 64.72, H 3.68, N 5.73%. IR (KBr pellet: cm ):
3
424(s), 1614(m), 1601(m), 1578(m), 1536(vs), 1433(m), 1404(m), 1306(w), 1205(w),
3

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1121(w), 994(w), 770(w), 708(w), 666(w), 553(w).
Xꢀray crystallography.
Suitable single crystals of complexes 1 and 2 were selected for indexing and
intensity data were measured on a Siemens Smart CCD diffractometer with
graphiteꢀmonochromated Mo Kα radiation (λ = 0.71073Å) at 298 K. The raw data
frames were intergrated into SHELXꢀformat reflection files and corrected using
2
2
SAINT program. Absorption corrections based on multi scan were obtained by the
23
SADABS program. The structures were solved with direct methods and refined with
fullꢀmatrix leastꢀsquares technique using the SHELXSꢀ97 and SHELXLꢀ97 programs,
24
respectively. Displacement parameters were refined anisotropically, and the
positions of the Hꢀatoms were generated geometrically, assigned isotropic thermal
parameters, and allowed to ride on their parent carbon atoms before the final cycle of
refinement. Basic information pertaining to crystal parameters and structure
refinement is summarized in Table 1, and selected bond lengths and angles are listed
in Table S1 in ESI. CCDC 1514291 (1) and 1514292 (2) contain the supplementary
crystallographic data for this paper. These data can be obtained free of charge from
The
Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
Result and discussion.
Crystal structure of {[Co(HL)(bpy)(H
2
O)
2
)]·DMF}
n
(1)
Single crystal Xꢀray diffraction indicated that compound 1 crystallizes in the
orthorhombic system with space group Pbca. As shown in Fig. 1a, the asymmetric
2
ꢀ
unit contains one independent Co atom, one HL ligand, one bpy ligand, two
coordinated aqua molecules and one free DMF molecule. Co1 is situated in a distorted
hexaꢀcoordinated octahedral geometry with CoO
4
N
2
coordination sphere. The four
2
ꢀ
oxygen atoms are from two different HL ligands (O1 and O9) and two different H
2
O
molecules (O7 and O8), while the two nitrogen atoms (N1 and N2) from two different
bpy linkers. The CoꢀO and CoꢀN bond lengths are in the range of 2.081(3)ꢀ2.170(4) Å.
The bpy ligand bridges with two adjacent Co centers to form a oneꢀdimensional chain
2
ꢀ
2+
along the aꢀaxis, and the partly deprotonated ligand HL connects two Co ions via
1
1
2
two chelating carboxyl groups through ꢀ : η : η coordination mode. The connections
2
ꢀ
of the Coꢀbpy chains withtheseHL ligands results into the formation of a
twoꢀdimensional wavelike sheet along the ab plane (Fig. 1b).The Co···Co distances
2
ꢀ
separated by bpy and HL ligands are 11.36 and 10.86 Å, respectively. Topologically,
4

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both the flexible Vꢀshaped carboxylate ligands and the cobalt centers could be viewed
as distorted tetrahedral 4ꢀconnected nodes, resulting into distorted (4,4)ꢀconnected sql
topology (Fig. 1c). Adjacent layers are further stacked along the c axis (Fig. S1a).
(a)
(b)
(c)
Fig. 1 (a) The asymmetry unit of compound 1. (b) Twoꢀdimensional layer of
compound 1 along the ab plane. (c) The (4,4)ꢀsql net of compound 1.
n
Crystal structure of {[Co(HL)(bpe)]·0.5bpe} (2)
Compound 2 crystallizes in the triclinic system with space group Pꢁ1, and also
displays a 2ꢀD framework but with different arrangement from compound 1. As
2
ꢀ
illustrated in Fig. 2a, the asymmetric unit has one Co atom, one HL ligand, one
coordinated bpe ligand, and a half free bpe molecule. Co1 is also hexaꢀcoordinated by
four oxygen atoms (O1, O2, O7A and O8) from two bidentateꢀchelate coordination
5

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carboxylates and two nitrogen atoms from bpe ligand. The CoꢀO and CoꢀN bond
lengths are in the range of 2.068(3)ꢀ2.257(3) Å. Two adjacent Co centers are joined by
2
ꢀ
1
1
1
1
2 2 2
two HL ligands inꢀ : η : η : η : η mode, forming a dimeric unit of [Co (HL) ] with
Co···Co separation of 7.15 Å (Fig. 2b).These units are further connected by two
crystallographically independent bpe molecules and extended into a 2ꢀD sheet along
the ab plane (Fig. 2c). The units are separated by bpe molecules with the Co···Co
2 2
distance of 13.55 and 13.57 Å, respectively. Topologically, the Co (HL) ] units could
be considered as nodes and bpe ligands as linkers. The whole topology can be
represented as (4,4)ꢀconnected sql net (Fig. 2d). The OꢀH···N interactions existing
between the carboxylate oxygen atom (O5) and free bpe nitrogen atom (N3) connect
these sheets, resulting in the overall 3ꢀD supramolecular architecture (Fig. S1b).
(a)
(b)
(c)
(d)
Fig. 2 (a) The asymmetry unit of compound 2. (b) The Coꢀcarboxylate dimer structure.
(
c) Perspective view of the 2ꢀD sheet of compound 2 along the ab plane. (d) The
4,4)ꢀsql net of compound 2.
(
Magnetic properties of compounds 1 and 2.
Directꢀcurrent (dc) SQUID magnetometry for compounds 1 and 2 were conducted
at an applied field of 1000 Oe and in the temperature range of 2ꢀ300K. Temperature
6

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dependence of the magnetic susceptibilities of these compounds in the form of χ
M
T
versus T was shown in Fig.3. Two compounds exhibited similar curves. The values of
3
ꢀ1
M
χ T at 300 K were 2.72 and 2.49 cm K mol for compound 1 and 2, respectively,
3
ꢀ1
7
II
both larger than the theoretical value of 1.875 cm K mol for one highꢀspin d Co ion
3
ꢀ1
with S = 3/2. These values both fall well in the range of 2.1ꢀ3.4 cm K mol for
II
experimentally observed highly anisotropic Co ions with a considerable contribution
2
5
M
from the orbital angular momentum. The χ T value shows a steady decrease with
3
ꢀ1
the decrease of the temperature, and reaches 6.92 and cm K mol at 1.8 K. The
decrease may be due to the spinꢀorbital coupling (SO coupling) and zeroꢀfield
splitting (ZFS) of the Co(II) ions.
Considering the large Co···Co separations (13.55 and 13.57 Å) within these 2ꢀD
frameworks, the magnetic exchange between the local spin carriers could be neglected.
The origin of magnetic properties is single ion properties of Co(II) ions. The total
Hamiltonian including spinꢀorbital coupling (SO coupling), crystalꢀfield interaction
ˆ
ˆ
ˆ
ˆ
and Zeeman perturbation can be written as:
H
= H + H + H
.
total
SO
CF
Zeeman
For 3d ion Co(II), only the first order SO coupling parameter is applied, so the
ˆ
ˆ
operator is given as
H
=
λσLS ,where λ is the SO coupling parameter and σ is the
SO
0
2
orbital reduction parameter. The crystal field parameters (CFPs) B2 and B2 should be
included in the fitting where the second order CFP is intimately related to the standard
0
2
ZFS parameters (axial ZFS parameter D = 3B2θ2 and rhombic one E = B2θ2
,
θk is the
Co
operator equivalent factor with rank k = 2 or 4 for 3d ions). The spin Hamiltonian is
2
2
2
1
2
2
ˆ
ˆ
ˆ
ˆ
ˆ
−
given as:
H
= D(3L − L )
σ
+ E[ (L + L )]
σ
The Zeeman term is
ZFS
Z
+
2
.
ˆ
ˆ
ˆ
H
=
ꢀ
B(gSI +
σ
LI )H ,where I is the identity matrix. The fitting process by
Zeeman
26
ꢀ1
PHI program with total Hamiltonian gave g = 2.21, σ= 0.654, λ = ꢀ171.5 cm D =
ꢀ1
ꢀ1
ꢀ
0.071 cm , E = ꢀ0.00088 cm and R = 0.18 for 1. The fitting results given by the
ꢀ1
ꢀ1
same Hamiltonian are g = 2.12, σ= 0.600, λ = ꢀ150 cm D = ꢀ0.076 cm , E = ꢀ0.021
ꢀ1
cm and R = 0.25 for 2. The SO coupling parameters are in the range of ꢀ180—ꢀ100
ꢀ1
27
cm for sixꢀcoordinated highꢀspin cobalt(II) complexes.
The relatively small D
values indicate weak magnetic anisotropy which is related to the energy barrier and
magnetic relaxation.
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(a)
(b)
Fig.3 Plots of χ T versus T for compounds 1 (a) and 2 (b). Inset: the experimental
M
plots of M versus H/T at different fields. The red solid lines are fitted data.
From the highꢀfield reduced magnetization data in the ranges of magnetic field
from 1 to 7 T and temperature from 10 to 1.8 K, M versus H/T curves of different
fields are not isolated clearly. This also demonstrates the weak magnetic anisotropy
with small D values and the lack of wellꢀdefined ground state. The field dependence
of the magnetization of at 2.0 K showed a gradual increase of the magnetization at
B
low fields and reaching 2.10 and 2.04 µ at 7 T, respectively (Fig. S3). The presence
of gradual increase and the lack of saturation all suggest the crossed energy levels of
2
5
microꢀstates influenced by Zeeman perturbation under applied field. The relatively
small D values deduced from the fitting result and the nearly overlapped reduced
magnetization curves in MꢁH/T plots can prove weak anisotropy which leads to
crossed energy levels of microꢀstates. The direct consequence is the levels of the
exited states and the ground state will cross with each other under low field. Thus
many more cross over will emerge as the field increase, which gives the MꢀH curve a
gradual feature.
Consequently, the ac susceptibility measurements of these two compounds were
further performed with a 2.0 Oe ac field oscillating at frequencies in the range of
1
ꢀ988 Hz and in the temperature range of 1.8ꢀ10 K. Interestingly, when a zeroꢀfield dc
field was employed, almost no obvious outꢀofꢀphase susceptibility ( ’’) was
observed(Fig. S4). When a static dc field of 2000 Oe was applied, however, both the
inꢀphase χ ’ and outꢀofꢀphase χ ’’ signals of the compounds were enhanced and
χ
M
M
M
significant frequencyꢀdependent outꢀofꢀphase signals with peaks were found (Fig. 4).
This difference indicates the quantum tunneling was quenched by a dc field. These
8

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behaviors are the essential characteristic of slow magnetization relaxation.
(a)
(b)
(c)
(d)
Fig.4 The temperature dependence of the inꢀphase (χ’) and outꢀofꢀphase (χ’’) ac
susceptibilities at different frequencies with an oscillation of 2000 Oe dc field for
compound1 ((a) and (b)) and 2((c) and (d)), respectively.
The relaxation data for 2000 Oe field exhibits a liner correlation complying with
the Arrhenius law [ln(1/2πf) = lnτ + ꢂ/k T]. By fitting the plot of ln(2πf) versus 1/T ,
0
B
p
the energy barrier ꢂ/k
B
and preꢀexponential factor τ
0
were obtained: ꢂ/k
B
= 13.87 K
ꢀ6
ꢀ5
and τ
0
= 8.98 ×10 s for compound 1, and ꢂ/k
B
= 8.70 K and τ
0
= 1.43 × 10 s for
compound 2, respectively (Fig.5a and 5b). The preꢀexponential factorvalues are
ꢀ7
ꢀ11
deviates slightly from the range typical of SIMs (10 ꢀ10 s), while the values are
II
28
comparable with those reported Co SIMs.
Furthermore, the magnetization relaxation of the compounds were confirmed from
the ColeꢀCole data of the inꢀphase (χ ’) versus outꢀofꢀphase (χ ’’) signals (Fig. 5c
M
M
and 5d). The Cole–Cole plots of both compounds exhibit an asymmetric semicircle
with the right one featuring almost a tail, indicating the presence of two
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closelyꢀspaced relaxation processes. Then the relaxations can be described by the sum
29
of two modified Debye functions:
(a)
(b)
(c)
(d)
Fig.5 Arrhenius and ColeꢀCole plots of compounds 1((a) and (c)) and2((b) and (d)) in
a 2000 Oe dc field.
The parameters α and τ are the width of the τ distribution and the relaxation time
constant, respectively. χS,tot = χS1 + χS2 represents the sum of the adiabatic
susceptibilities of the two relaxing species; ꢁχ is the difference between the adiabatic
i
susceptibility (χSi) and the isothermal susceptibility (χTi) of each magnetic phase. The
experimental χac(ω) curves between 1.8 and 6.0 K can be nicely simulated by the
equation (Table S2 and S3). For each temperature, the right incomplete part
corresponding to a lowꢀfrequency domain could be assigned to slower relaxation (SR)
1 1
dynamics with parameters α and τ and the left one corresponding to a
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2 2
highꢀfrequency one are the faster relaxation (FR) dynamic with parameters α and τ .
The total AC susceptibility χAC(ω) = χ
two vectors χ and χ following the parallelogram law for addition, and conversely,
AC can be resolved into its components χ and χ . This reveals that the shape of the
Cole–Cole plots for the overall process are mainly determined by the different
relaxation times of each process. Under 1.8 K, the values of τ /τ (0.221/0.00225 ≈
8.22 for compound 1, and 0.051/0.00096 ≈ 53 for compound 2) are both in the range
1
(ω) + χ
2
(ω) is geometrically constructed by the
1
2
χ
1
2
1
2
9
3
0
of 10ꢀ100, indicating two merged semicircles.
Catalytic activities of compounds 1 and 2.
With the aim to understand the catalytic property of these coordination compounds
for developing a new oxidation system in organic chemistry, the oxidation of
diphenylmethane to benzophenone was selected as a model reaction (Scheme 1). As
shown in the Fig. 6, compound 2 showed moderate activities while compound 1
presented superior activity toward the oxidation reaction, with the latter giving 90.3%
conversion and 98.1% selectivity in chlorobenzene at 80°C for 24h. These
preliminary results exhibited that these compounds could facilitate the oxidation of
diphenylmethane and serve as selective and efficient catalyst. Structurally, the higher
catalytic activity of compound 1 may probably be attributed to the coordination aqua
molecules around Co ions not carboxylate oxygen atoms, which may lead to lower
steric hindrance and leave enough space for the substrates and functions as potential
active sites for oxidation through the departure of water molecules.
Scheme 1. Oxidation of diphenylmethane using four catalysts under the preliminary
optimization conditions.
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Fig. 6 Conversion of diphenylmethane to benzophenone with different catalysts.
Reaction condtions: diphenylmethane (0.125 mmol), catalysts (10
chlorobenzene (0.5 mL), TBHP (0.375 mmol), 80 ºC, 24h.
µmol),
Then, optimization of the reaction conditions were carried out by selectively
evaluating effects of different diphenylmethaneꢀtoꢀcatalysts molar ratios,
oxidantꢀtoꢀcatalysts molar ratios, and the amount of solvent used. The results were
listed in Table S4 in Supporting Information. One can see that both two compounds
can promote the catalytic oxidation of diphenylmethane, leading to benzophenone and
diphenylmethanol with preferable selectivity of the carbonyl product. On the basis of
the oxidation of diphenylmethane, 3 equiv of TBHP and 10 µmol of catalyst were
appropriate for all catalytic reactions. Utilizing these optimized reaction conditions,
the reaction scope by employing a variety of benzylic CꢀH compounds was
subsequently explored. As illustrated in Table 2, the corresponding ketones with aryl
side chain groups were successfully synthesized from corresponding benzylic CꢀH
compounds in great conversion rate (90.3ꢀ99%) and exceptional selectivity (98.1ꢀ99%)
by using compound 1 as the catalyst. That is to say, compound 1 could facilitate the
oxidation of benzylic CꢀH bonds and may serve as highly efficient and selective
catalyst.
12

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DOI: 10.1039/C6DT04551K
Fig. 7. Recycle experiments of compound 1 on oxidation of diphenylmethane.
Reaction conditions: diphenylmethane. (0.125 mmol), compound 1 (10 µmol),
chlorobenzene (0.5 mL), tꢀBuOOH (0.375 mmol), 80 ºC, 24 h.
Recyclability is an important and essential feature for any catalyst to be considered
in largeꢀscale catalytic reactions. As shown in Fig. 7, after completion of the oxidation
reaction, the catalyst can easily be separated from the reaction mixture. The recovered
2 2
catalyst was reꢀactivated by washing with CH Cl three times and further reused
directly in a subsequent oxidation of benzylic CꢀH bonds reaction. The catalytic
st
activity did not decrease after five catalytic cycles (1 run, Conv. 90.3%, Sele. 98.1%;
nd
rd
th
2
8
run, Conv. 89.5%, Sele. 98.4%; 3 run, Conv. 89.9%, Sele. 97.6%; 4 run, Conv.
th
8.7%, Sele. 98.2%; 5 run, Conv. 88.2%, Sele. 97.9%); and the IR of the recovered
compound 1 are identical to those of the freshly prepared samples (Fig. S5).
Conclusion.
Two 2ꢀD cobalt(II) compounds have been synthesized using a multicarboxylate
phenolic carboxylic acid and different Nꢀdonor ligands. Both compounds exhibit 2ꢀD
wavelike and double layered arrangement, respectively. These compounds both
exhibit fieldꢀinduced singleꢀion relaxation magnetization and exceptional catalytic
activities of benzylic CꢀH oxidation, and could be viewed as multifunctional
materials.
13

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DOI: 10.1039/C6DT04551K
Supporting Information.
Xꢀray crystallographic data in CIF format (CCDC, 1514291 and 1514292), PXRD,
and additional magnetic as well as catalytic data. Supporting Information is available
free of charge on the ACS Publications website at DOI: 10.1021/acs. inorgchem.
Acknowledgements.
We are thankful to the National Natural Science Foundation of China (No.
2
1571092, 21401094, 21571112 and 21403102), the Natural Science Foundation of
Shandong Province (No. ZR2012BQ023), and the University Scientific Research
Development Plan of the Education Department of Shandong Province (No.
J14LC10).
Table 1. Refinement of the crystal structures of compounds 1 and 2.
Compound
formula
formula weight
T (K)
1
2
C H CoN O
3
4
31
3
11
C H CoN O
8
39 27
3
716.55
724.57
298(2)
298(2)
Crystal system
Space group
a [Å]
Orthorhombic
Pbca
Triclinic
Pꢁ1
16.6121(15)
15.1060(14)
26.457(2)
90
9.8280(8)
13.1261(11)
14.0239(12)
91.9290(10)
106.802(2)
100.302(2)
1697.0(2)
2
b [Å]
c [Å]
α [˚]
β [˚]
90
γ [˚]
90
3
V [Å ]
6639.2(10)
8
Z
ꢀ3
D
calcd. [g·cm ]
1.434
1.418
ꢀ1
ꢀ
[mm ]
0.583
0.565
θ range
2.39ꢀ25.02
2.28ꢀ25.02
ꢀ6<=h<=11
ꢀ15<=k<=15
ꢀ16<=l<=15
ꢀ
19<=h<=19
13<=k<=17
index ranges
ꢀ
ꢀ31<=l<=31
R
1
;wR2a [I> 2σ(I)]
0.0694; 0.1885
1.047
0.0604; 0.1444
1.020
GOF
14

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DOI: 10.1039/C6DT04551K
[
a]
Table 2. The oxidation of benzylic CꢀH bonds catalyzed by compound 1.
[b]
Entry
Substrates
Products
Conv. (%) Sele. (%).
1
90.3
>99
98.1
>99
2
3
4
5
>99
>99
>99
>99
>99
>99
[
(
a]Reaction conditions: Benzyl hydrocarbons (0.125 mmol), Coꢀbpy (10ꢂmol), chlorobenzene
0.5 mL), TBHP (0.375 mmol), 80ºC,24h. [b] Selectivity to ketones.
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Two 2-D multifunctional cobalt(II) compounds were reported with both
field-induced single-ion magnetism and catalytic oxidation of benzylic C-H bonds.