Synthesis and characterization of cobalt(iii) cyanide complexes: Cobalt participation in the decomposition of radical anion of TCNQ

Article abstract of DOI:10.1039/c2ce26095f

Reaction of Co(CH₃COO)₂·4H₂O, KTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) with the racemic or chiral H ₂salency (N,N′-bis(salicylidene)-1,2-cyclohexanediamine) ligand afforded three Co(iii) complexes K[Co(salency)(CN)₂]·CH ₃OH (1), K[Co(S,S-salency)(CN)₂]·H₂O (1S) and K[Co(R,R-salency)(CN)₂]·CH₃OH (1R), which have been fully characterized. The cyanide groups in these three complexes are generated from the in situ decomposition of the radical anion of TCNQ with the participation of cobalt(ii). Single-crystal X-ray diffraction analysis reveals that complex 1 exhibits an infinite double stair-like chain structure. However, the chiral complexes 1S and 1R show chain structures consisting of two independent sub-chains. All of these chains are bridged by the K⁺ ions, with the cyanides interacting with K⁺ in the end-on and unusual side-on π-type mode. Second-order nonlinear optical effect studies in the solid state revealed that 1S and 1R are SHG active. The Royal Society of Chemistry.

Full text of DOI:10.1039/c2ce26095f

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PAPER
Synthesis and Characterization of Cobalt(Ш) Cyanide Complexes:
Cobalt Participate in the Decomposition of Radical Anion of TCNQ
a,b
a,b
a,b
a,b
a
a
ChunꢀHong Tan , Xiao Ma , QiꢀLong Zhu , YiꢀHui Huang , YueꢀHong Wen , ShengꢀMin Hu ,
a,
TianꢀLu Sheng * and XinꢀTao Wu
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
Reaction of Co(CH COO) •4H O, KTCNQ (TCNQ =7,7,8,8ꢀTetracyanoquinodimethane) with the
3
2
2
racemic or chiral H salency (N,N’ꢀBis(salicylidene)ꢀ1,2ꢀ cyclohexanediamine) ligand afforded three
2
1
0
Co(Ш) complexes K[Co(salency)(CN) ]•CH OH (1), K[Co(S,Sꢀsalency)(CN) ]•H O(1S) and K[Co(R,Rꢀ
2
3
2
2
salency)(CN) ]•CH OH (1R), which have been fully characterized. The cyanide groups in these three
2
3
complexes are generated from the in situ decomposition of the radical anion of TCNQ with the
participation of cobalt(II). Singleꢀcrystal Xꢀray diffraction analysis reveals that complex 1 exhibits infinite
double stairꢀlike chain structure. However, the chiral complexes 1S and 1R show chain structures
+
1
5
consisting of two independent subꢀchains. And all of these chains are bridged by the K ions, with the
+
cyanides interacting with K in the endꢀon and unusual sideꢀon πꢀtype mode. Secondꢀorder nonlinear
optical effect studies in the solid state revealed that 1S and 1R are SHG active
.
Introduction
TCNQ with amines, chemists also discovered that the cyanide
group can be displaced by nitrite ion or (H O/O ) to give an
2
2
22, 25ꢀ34
5
5
6
6
0
5
0
5
orangeꢀred salt.
With all this in mind, we tried to synthesis
2
2
3
3
4
4
0
5
0
5
0
5
Nonlinear optical materials play a major role in the field of
photonics including optical information processing, sensor
NLO materials with intriguing architectures by the reaction of
KTCNQ, Co(CH COO) •4H O and H salency. However, we got
3
2
2
2
1
ꢀ
protector applications, data storage, laser technology and so on.
three unexpected complexes with the cyanide groups other than
13
It has been reported that some chiral coordination complexes
the TCNQ ligands, K[Co(salency)(CN) ]•CH OH (1), K[Co(S,Sꢀ
2
3
exhibit large NLO response, several orders of magnitude larger
than widely known inorganic materials. Meanwhile, the chiral
coordination complexes show intriguing variety of architectures
salency)(CN) ]•H O (1S), K[Co(R,Rꢀsalency)(CN) ]•CH OH
2
2
2
3
(
1R). The three complexes maybe resulted from the redox
2+
- ·
reaction of Co and TCNQ
decomposition of TCNQ
as well as the consequent
1
4ꢀ17
and topologies.
Thus the synthesis and characterization of
-·28, 35ꢀ38
. These are the first examples of
chiral inorganicꢀorganic materials have received considerable
attention in recent years.
The two most often used methods to obtain chiral species are by
stereoselective synthesis using chiral species or by spontaneous
resolution upon crystallization without any chiral auxiliary.
To prepare new chiral complexes, we focus our attention on
TCNQꢀbased complexes incorporated organic auxiliary ligands
cobalt cyanide complexes obtained from the lost cyanide groups
of TCNQ and these also can put a new insight into the
decomposition of TCNQ. All these complexes exhibit infinite
+
chain structures which are bridged by K ions and secondꢀorder
1
8ꢀ21
nonlinear optical effect studies in the solid state revealed that
chiral complexes 1S and 1R are SHG active with a weak signal.
Herein, we report the details of the syntheses, structures and
properties of the three complexes.
H salency(N,N’ꢀBis(salicylidene)ꢀ1,2ꢀcyclohexanediamine) with
2
optical activity. TCNQ (7,7,8,8ꢀtetracyanoꢀpꢀquinodimethane) is
a wellꢀknown multiꢀredox active ligand.
groups allows variable coordination to a transition metal in
monoꢀ, biꢀ, triꢀ, and tetraꢀdentate binding modes, offering great
flexibility in the selfꢀassembly of interesting clusters and
extended networks. While the electron affinity enables facile
2
2ꢀ24
The four C≡N
Experimental section
Materials and methods
reduction by electronꢀrich metal complexes to form related 70 All chemicals were reagent grade and used without further
39, 40
28
radical anions and dianions. Moreover, it has been found that
certain primary and secondary amines can react with TCNQ to
give products in which one or two cyanide groups are replaced by
the amine. In addition to the displacement of cyanide groups of
purification. H
2
salency
and KTCNQ were prepared as
reported procedures. Elemental analyses of C, H and N were
performed with a Vario MICRO CHNOS Elemental Analyzer.
The FTꢀIR spectra were recorded on a PerkinꢀElmer Spectrum
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

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–1
One Spectrometer using KBr pellets in the range of 4000–400
cm . Powder Xꢀray diffraction data were collected using a
MiniFlexII powder diffractometer equipped with Cu Kα radiation
(w), 757 (s), 738 (w)，694 (w), 567 (w) cm .
–1
60
K[Co(R,Rꢀsalency)(CN) ]•CH OH (1R)
2 3
(
λ = 1.54056 Å). Circular dichroism (CD) spectra were conducted
This complex was prepared by the similar method as for 1. Yield:
4.9 mg (34.7% based on Co). C H CoKN O (502.49): Calcd.
5
on a Jasco Jꢀ810 spectrodichrometer. Electrospray ion mass
spectra (ESI−MS) were performed on DECAXꢀ30000 LCQ Deca
3
23 24
4
3
XP Ion Trap Mass Spectrometry. The ESR spectra were acquired 65 C 54.98, H 4.81, N 11.15; found C 55.13, H 4.48, N 11.75. IR
on a Bruker ERꢀ420 spectrometer.
(KBr): 3470 (br), 2945 (m), 2866 (w), 2147 (w), 2121 (m), 1639
s), 1595 (s), 1533 (m), 1469 (m), 1450 (s), 1387 (w), 1348 (m),
320 (m), 1225 (w), 1197 (w), 1150 (w), 1126 (w), 1044 (w), 907
(
1
10
Synthetic procedures
–1
(w), 756 (s), 739 (w)，695 (w), 564 (m) cm
.
Resolution of (±)transꢀ1,2ꢀDiaminocyclohexane
70
Xꢀray crystallography
Lꢀ(+)ꢀtartaric acid 15 g ( 0.1 mmol) in 50 ml distilled water was
stirred at 70 °C for 15 mins, then (±)transꢀ1,2ꢀ
diaminocyclohexane 24 ml (0.2 mol) was added in 30 mins. After
Single crystals for 1, 1S and 1R were mounted on glass fibers.
Cell constants and data collections were performed on a Rigaku
Mecury CCD diffractometer equipped with graphiteꢀ
15
2
h, 10 ml glacial acetic acid was added in the resulting solution
and a white precipitate formed immediately. The slurry was 75 monochromated MoꢀKα radiation source (λ = 0.71073 Å) by ω
vigorously stirred for 2 h and cooled to room temperature. The
precipitate was collected by filtration, washed with ice water,
methanol, diethyl ether and dried in air. Yield: 19.9 g (79.0%).
scan mode. The structures were solved by the direct method using
the SHELXTL Version 5 package of crystallographic software,
2
2
0
and refined with a fullꢀmatrix leastꢀsquares refinement on F .
Metal atoms were located from the Eꢀmaps and refined
80 anisotropically. The other nonꢀhydrogen atoms were located by
the difference Fourier maps basing on these atomic positions and
refined anisotropically. Hydrogen atoms were added according to
the theoretical models. Pertinent crystal data and structure
refinement results are summarized in Table 1, and their selected
(R,R)ꢀN,N’ꢀBis(salicylidene)ꢀ1,2ꢀcyclohexanediamine
2
The above mentioned product (5.947 g, 0.0225 mol), K CO3
25
(6.216 g, 0.0450 mol) were dissolved in 30 ml distilled water.
Salicylaldehyde (4.74 ml, 0.0225 mol) in 20 ml ethanol was
added in 30 mins. The resulting yellow slurry was stirred at reflux 85 bonds lengths and angles are provided in Tables S1–S3,
for 6 h and then cooled slowly. The product was collected by
filtration, washed with ice water and ethanol. This crude solid
was dissolved in CH Cl and washed with water. After drying
respectively.
3
3
4
0
5
0
2
2
Results and discussion
over Na SO , the solvent was removed under vacuum and yellow
2
4
Description of the structure
oil was obtained. Yield: 3.52 g, 48.6%. The ligands H salency
2
and (S, S)ꢀH salency are prepared in a similar way.
2
90
Complexes 1, 1S and 1R were fully characterized by Xꢀray
crystallography. Singleꢀcrystal Xꢀray structural analysis reveals
that complex 1 exhibits a 1D chain structure. The selected bond
lengths and angles for complexes 1 are given in Table S1,
Complex 1 consists of the units of [Co(salency)(CN) ] , K ions
2
95 and methanol molecules. The Co(III) ion in the octahedral
K[Co(salency)(CN) ]•CH OH (1)
2
3
A mixture of Co(CH COO) •4H O (0.0498 g, 0.2 mmol),
3
2
2
H salency (0.0644 g, 0.2 mmol), KTCNQ (0.0408 g, 0.2 mmol)
ꢀ
+
2
and CH OH (8 mL) was stirred at room temperature for 1 h and
3
placed in a Teflonꢀlined stainless container. The mixture was
heated at 80 °C for 3 days, and then cooled to room temperature
for 33 h. Red blockꢀshaped crystals suitable for Xꢀray analysis
were obtained, washed with distilled water and dried in the air.
Yield: 49.8 mg (49.6% based on Co). C H CoKN O (502.49):
ꢀ
monoanion [Co(salency)(CN) ] is lowꢀspin and sixcoordinated
2
by two equatorial nitrogen atoms and two equatorial oxygen
atoms from the tetradentate Schiffꢀbase ligand, and two axial
carbon atoms from the two cyanide groups. The CoꢀN distances
100 are 1.892(3) Å for Co1ꢀN1, 1.894(3) Å for Co1ꢀN2. The Co1ꢀO1
and Co1ꢀO2 distances are 1.915(3) and 1.910(3) Å, respectively.
The bond lengths of CoꢀC are 1.944(4) and 1.932(4) Å,
respectively, which are slightly longer than the CoꢀO and CoꢀN
bond lengths, indicating the slightly distorted octahedron
05 coordination sphere of the Co(III) ion. The CꢀN distances in the
axial cyanide groups are 1.136(5), 1.148(5) Å. The Co1ꢀC21≡
N3 and Co1ꢀC22≡N4 are in a good linear conformation with the
angles of 178.6(4) and 178.5(4) °.
2
3
24
4
3
45
Calcd. C 54.98, H 4.81, N 11.15; found C 54.96, H 4.36, N 11.70.
IR (KBr): 3478 (br), 2948 (m), 2863 (w), 2144 (w), 2118 (m),
1
638 (s), 1599 (s), 1538 (m), 1466 (m), 1452 (s), 1385(w), 1348
(
(
m), 1320 (m), 1220 (w), 1195 (w), 1150 (w), 1126 (w), 1044
w), 906 (w), 756 (s), 738 (w)，694 (w), 567 (m) cm .
–
1
1
50
K[Co(S,Sꢀsalency)(CN) ]•H O (1S)
2
2
This complex was prepared by the similar method as for 1. Yield:
5.6 mg (36.5% based on Co). C H CoKN O (488.47): Calcd.
It is notable that the kalium ions are linkers playing an
10 important role for the 1D doubleꢀstair like chain structure of
complex 1. Each kalium ion interacts with three discrete
3
22
22
4
33
1
55
C 54.10, H 4.54, N 11.47; found C 54.84, H 4.52, N 11.47. IR
(
(
KBr): 3482 (br), 2943 (m), 2864 (w), 2141 (w), 2118 (m), 1639
s), 1600 (s), 1538 (m), 1469 (m), 1453 (s), 1384 (w), 1347 (m),
ꢀ
[
[
Co(salency)(CN)2]
Co(salency)(CN) ] units are held together by the bridging K
units.
Consequently,
all
the
ꢀ
+
2
1
321 (m), 1223(w), 1196 (w), 1151 (w), 1126 (w), 1046 (w), 906
2
| Journal Name, [year], [vol], 00–00
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Table 1 Crystal data and structure refinements for 1, 1S and 1R.
Polymer
1
1S
1R
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
C H CoKN O
502.49
Monoclinic
C H CoKN O
488.47
C H CoKN O
3
502.49
2
3
24
4
3
22 22
4
3
23 24
4
Monoclinic
P21
13.873(15)
8.124(9)
19.53(2)
90.00
Monoclinic
P21
13.969(10)
8.164(5)
19.974(13)
90.00
P2 /c
1
13.449(5)
21.788(8)
8.202(3)
90.00
β (°)
γ (°)
V (Å )
Z
101.794(7)
90.00
2352.8(15)
4
91.96(2)
90.00
2200(4)
4
92.823(13)
90.00
2275(3)
4
3
T (K)
293(2)
1.419
0.938
1040
2.09–27.47
4268
293(2)
1.475
1.000
1008
2.51–27.39
5498
293(2)
1.467
0.970
1040
4.01ꢀ26.01
6560
3
D (g/cm )
c
–
1
ꢀ
(mm )
F(000)
θ range [°]
2
Unique reflections (Rint)
(
0.0359)
(0.0422)
1.024
(0.0407)
0.968
2
GOF (F )
1.122
Flack parameter
Final R indices [I > 2σ(I)]
Final R indices (all data)
ꢀ0.04(2)
0.04(3)
a
R = 0.0604, wR = 0.1749
R = 0.0676, wR = 0.1789
R = 0.0583, wR = 0.1303
1
2
1
2
1 2
a
R = 0.0746, wR = 0.1845
R = 0.1018, wR = 0.2144
1
R = 0.0932, wR = 0.1523
1
1
2
2
2
CCDC
859524
859525
859526
a
2
o
2
c
2
2
o
2
1/2
R
1
= ∑(F
o
– F
c
)/∑F
o
; wR
2
= [∑w(F
– F
) /∑w(F
) ]
+
15
As shown in figure 3, the K ion interacts with a pair of cyanide
groups in a sideꢀon manner, a N atom from the endꢀon cyanide,
four O atoms from the Schiffꢀbase ligands. The KꢀN, KꢀO and Kꢀ
C average separations in this interaction are 3.032, 2.951 and
3
.042 Å, respectively, comparable to those observed in the few
+
41ꢀ45
20
other K complexes of this type.
5
Fig. 1 view of doubleꢀstair like chain structure of complex 1 (Ni
turquoise, K green, O red, N blue, C gray).
atoms (Fig.1). Interestingly, although the Schiffꢀbase ligands
possess the same coordination mode, they are arranged in
different geometry configurations. The pair of enantiomers are
situated alternately in the chain (Fig.2).
Fig. 3 Asymmetric unit of complex 1, with some additional symmetryꢀ
equivalent atoms included to complete the coordination spheres around
the metal atoms.
25
1
0
Complexes 1S and 1R are enantiomers and crystallized in the
chiral space group P2 . Since 1S and 1R are a pair of enantiomers
1
(
(
Fig.4), only the crystal structure of 1S is described in detail here
The structure of complex 1R is shown in Fig. S1 and S2). Some
30
important bond parameters and angles for complexes 1S and 1R
are listed in Table S2ꢀS3. For complex 1S, the CꢀN distances in
the axial cyanide groups are in the range of 1.153ꢀ1.190 Å, the
Co1ꢀC21≡N6, Co1ꢀC22≡N5, Co2ꢀC44≡N7 and Co2ꢀC45≡
Fig. 2 The pair of enantiomers in complex 1.
This journal is © The Royal Society of Chemistry [year]
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N8 are in a good linear conformation with the angles of 177.9(8),
78.0(9), 175.3(1) and 178.9(9)° respectively. Similarly, for
1
complex 1R, the CꢀN distances in the axial cyanide groups range
from 1.125 to 1.146 Å, the Co1ꢀC21≡N6, Co1ꢀC22≡N5, Co2ꢀ
C44 ≡ N7 and Co2ꢀC45 ≡ N8 are also in a good linear
conformation with the angles of 174.6(7), 177.3(9), 175.0(9) and
5
1
78.7(8)°, respectively. All the distances and angles are in the
39, 40
normal range.
10
Fig. 4 The pair of enantiomers in complexes 1S (left) and 1R (right). The
+
axial cyanide groups, bridging K ions and hydrogen atoms have been
omitted for clarity.
Fig. 6 view of chains in complex 1S (Ni turquoise, K green, O red, N
blue, C gray).
The crystal structure of complex 1S is shown in Fig.5. The
Co(III) ion similar to that in complex 1, is also lowꢀspin and
sixcoordinated with a Schiffꢀbase ligand and two axial cyanide
15
20
25
30
35
groups, with normal bond distances and angles. Unlike complex 45 Optical spectra and NLO properties
1
, the asymmetry unit of complex 1S consists of two monoanion
The infrared spectrum of 1 shows two ν(C≡N) stretches at 2144
ꢀ
+
[
Co(S,Sꢀsalency)(CN) ] , two K ions and two water molecules.
2
ꢀ1
and 2118cm , consistent with the presence of both the terminal
+
It should be noted that the bridging interactions around the K
ions are different. K1 and K2 each interact with two sideꢀon
cyanides, one water molecule, four oxygen atoms in Schiffꢀbase
ligand and one additional cyanide ligand via the N atoms only,
with the KꢀN and KꢀC sideꢀon interactions averaging 3.250 and
3.135 Å for K1, 3.215 and 3.118 Å for K2 respectively. The
41, 46ꢀ49
and bridging cyanide groups.
Complexes 1S and 1R show
no significant difference in the infrared spectrum and they have
similar absorption in the same region as complex 1.
5
5
6
0
5
0
Complexes 1S and 1R crystallize in the chiral monoclinic
space group with flack parameters of ꢀ0.04(2) and 0.04(3)
respectively.The circular dicrhrosim (CD) spectra in KBr pellets
were mearsured to confirm the optical activity and the
enatiomeric nature of these complexes. The CD spectrum for 1S
shows a mirror image of that for 1R at a similar wavelength
confirming that complexes 1S and 1R are enantiomers of each
other (Fig.7). The outcomes are in accord with the structures
obtained by single crystal Xꢀray diffraction. Besides, complexes
1S and 1R exhibit secondꢀorder nonlinear optical (NLO) effect as
expected. Powdered samples of 1S and 1R are SHG active with a
weak signal.
combination of multiply bridging cyanide ligands, as well as the
+
bridging oxygen atoms between the
K
ions, results in
propagation of the structure into a 1ꢀD chain with two subꢀchains
+
(
Fig.6). Meanwhile, the interaction between the K ions and the
surrounding atoms in complex 1R are almost the same as that of
complex 1S except the absence of water molecules. And the KꢀN
and KꢀC separations in the sideꢀon interactions average 3.295 and
3
.147 Å for K1, 3.225 and 3.097 Å for K2 respectively, and all
+
these interactions between the K ions and the sideꢀon cyanides
are also comparable to those in previous reports.
4
1ꢀ45
Fig. 5 Asymmetric unit of complex 1S, with some additional symmetryꢀ
equivalent atoms included to complete the coordination spheres around
the metal atoms.
Fig. 7 The solidꢀstate CD spectra of bulk samples 1S and 1R
.
40
4
| Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

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About in situ synthesis
these reactions throws new light on the dicompositon of radical
anion of TCNQ and provides a new method to synthesize metal
cyanide complex. Complex 1 exhibits infinite double stairꢀlike
chain structure. However, the chiral complexes 1S and 1R show
novel chain structures consisting of two independent subꢀchains.
The reaction of KTCNQ, Co(CH COO) ꢁ4H O and H salency in
methanol provided an unexpected different result and three novel
complexes containing [Co(CN) (salency)] units linked by K
ions were produced (scheme 1).
3
2
2
2
ꢀ
+
2
45
5
+
And all of these chains are bridged by K ions with unusual
interations. Secondꢀorder nonlinear optical effect studies in the
solid state revealed that 1S and 1R are SHG active with a weak
signal.
50
Acknowledgements
This work was supported by grants from the 973 Program
(2012CB821702), the National Science Foundation of China
Scheme 1 The synthetic route of 1, 1S and 1R.
(
21073192, 20871114 and 21173223), the Science Foundation of
Considering the typically similar reactivity of TCNQ molecule,
the reaction here is quite different. In the absence of amines and
nitrite ions, the participation of cobalt put a new insight into the
route of TCNQ decomposition. The possible mechanism of the
unusually reaction is illustrated by scheme 2. The electronꢀrich
coordination complex Co(salency) with the equatorial inplane
tetradentate Schiffꢀbase ligand was formed at first. While TCNQ
is a wellꢀknown multiꢀredox active ligand and KTCNQ can
CAS (KJCX2ꢀYWꢀH20) and of Fujian Province (2009HZ0006ꢀ1).
1
1
2
2
3
0
5
0
5
0
5
5
Notes and references
a
State Key Laboratory of Structure Chemistry, Fujian Institute of
Research on the Structure of Matter, Chinese Academy of Sciences,
Fuzhou, 350002, China. Eꢁmail: tsheng@fjirsm.ac.cn;
Fax: +86ꢁ591ꢁ83719238; Tel: +86ꢁ591ꢁ83719238
6
6
7
7
8
8
9
9
0
5
0
5
0
5
0
5
-·
b
proceed redox reaction with Co(salency). TCNQ (KTCNQ) was
Graduate School of the Chinese Academy of Sciences, Beijing,
2ꢀ
reduced by Co(salency) and further formed its dianion TCNQ .
100049, China
†
2
+
3+
Electronic Supplementary Information (ESI) available: supplementary
Meanwhile, the Co was oxidized into Co , this was confirmed
figures, tables and XRD. CCDC 849524ꢀ849526. For ESI and
crystallographic data in CIF or other electronic format, See
DOI: 10.1039/b000000x/
by the fact that all the final complexes 1, 1S and 1R show no
2
ꢀ
EPR signals. And then, in the presence of O , TCNQ lost the
2
3+
ꢀ
CN groups which were transferred to the Co center and turned
into the stable product DCTC (α,αꢀdicyanoꢀpꢀtoluoylcyanide
ꢀ
1. J.ꢀR. Li, Y. Tao, Q. Yu, X.ꢀH. Bu, H. Sakamoto and S. Kitagawa,
Chemistry ꢁ A European Journal, 2008, 14, 2771ꢀ2776.
2. M. Du, X.ꢀH. Bu, Y.ꢀM. Guo, J. Ribas and C. Diaz, Chem. Commun.,
22, 28, 29, 31, 46, 50ꢀ53
ꢀ
anion).
1, 1S and 1R was supported by the typical infrared absorption of
CN in the IR spectra and the element analyses of the three
The existent of CN groups in complexes
2
002, 2550ꢀ2551.
ꢀ
3
.
M. Du, X.ꢀH. Bu, Y.ꢀM. Guo, H. Liu, S. R. Batten, J. Ribas and T. C.
ꢀ
complexes. The orangeꢀred powder byꢀproduct DCTC salt
formed in the reactions was confirmed by the MS analysis (m/z
for C N OH calcd 194.2, found 194.8) and the infrared study
W. Mak, Inorg. Chem., 2002, 41, 4904ꢀ4908.
4. R. Santhakumari, K. Ramamurthi, H. StoeckliꢀEvans, R. Hema and
W. Nirmala, Physica B: Condensed Matter, 2011, 406, 1872.
5. X. H. Ma, L. M. Fu, Y. Zhao, X. C. Ai, J. P. Zhang, Y. Han and Z. X.
Guo, J. Polym. Sci., Part B: Polym. Phys., 2011, 49, 649.
11
3
4
ꢀ
1
revealed both the existence of the carbonyl group (1640 cm ) and
ꢀ
1
ꢀ 32, 39
the cyanide group (2133ꢀ2194 cm ) of DCTC
Thus, the
6
.
D. Senapati, T. Senapati, P. S. Wate, R. Kanchanapally, Z. Fan, A.
2+
ꢀ
reaction of Co , H salency and CN from KTCNQ provided
anion [Co(CN) (salency)] . Furthermore, the counter K cations
Kumar Singh and P. Chandra Ray, Chem. Commun., 2012, 48, 6034.
2
ꢀ
+
7. L. Cheng, L. Zhang, S. Gou, Q. Cao, J. Wang and L. Fang,
2
Crystengcomm, 2012, 14, 3888.
help to selfꢀassemble complexes into a 1D chain structures.
8
9
.
.
H. J. Zhao, X. T. Wu and L. M. Wu, Struct. Bond, 2012, 145, 121.
A. P. Higginbotham, J. M. Cole, M. A. BloodꢀForsythe and D. D.
Hickstein, J. Appl. Phys., 2012, 111, 033512.
10. S. r. R. Domingos, P. S. P. Silva, W. J. Buma, M. H. Garcia, N. C.
Lopes, J. A. n. Paixão, M. R. Silva and S. Woutersen, The Journal of
Chemical Physics, 2012, 136, 134501.
1
1. Y. Y. Yin, J. G. Ma, Z. Niu, X. C. Cao, W. Shi and P. Cheng, Inorg.
Chem., 2012, 51, 4784.
12. P. Yu, L. J. Zhou and L. Chen, J. Am. Chem. Soc., 2012, 134, 2227.
1
3. X. M. Jiang, M. J. Zhang, H. Y. Zeng, G. C. Guo and J. S. Huang, J.
Am. Chem. Soc., 2011, 133, 3410.
4. Z. Guo, R. Cao, X. Wang, H. Li, W. Yuan, G. Wang, H. Wu and J.
Li, J. Am. Chem. Soc., 2009, 131, 6894.
1
15. J. Madhavan, S. Aruna, K. Prabha, J. P. Julius, G. P. Joseph, S.
3
5
Selvakumar and P. Sagayaraj, J. Cryst. Growth, 2006, 293, 409.
1
1
1
1
6. A. Kandasamy, R. Siddeswaran, P. Murugakoothan, P. S. Kumar and
R. Mohan, Crystal Growth & Design, 2006, 7, 183.
7. X. N. Jiang, D. Xu, D. Yuan, M. Lu, S. Guo, G. Zhang, X. Wang and
Q. Fang, J. Cryst. Growth, 2001, 222, 755.
Scheme 2 Schematic representation of the in situ reactions.
100
Conclusions
8. E. Q. Gao, S. Q. Bai, Z.ꢀM. Wang and C. H. Yan, J. Am. Chem. Soc.,
2
003, 125, 4984.
In summary, we got three cobalt(III) cyanide complexes which
9. E. Q. Gao, Y. F. Yue, S. Q. Bai, Z. He and C. H. Yan, J. Am. Chem.
Soc., 2004, 126, 1419.
-
·
4
0
are obtained from the cyanide groups of TCNQ . The study of
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 5

CrystEngComm
Page 6 of 7
View Online
2
2
0. I. De Cat, Z. Guo, S. J. George, E. W. Meijer, A. P. H. J. Schenning
and S. De Feyter, J. Am. Chem. Soc., 2012.
1. D. J. Smith, G. P. A. Yap, J. A. Kelley and J. P. Schneider,
J.Org.Chem., 2011, 76, 1513.
75
5
0
5
0
5
0
5
0
5
0
5
0
5
0
22. S. Shimomura, R. Matsuda, T. Tsujino, T. Kawamura and S.
Kitagawa, J. Am. Chem. Soc., 2006, 128, 16416.
2
2
2
2
3. H. Miyasaka, T. Izawa, N. Takahashi, M. Yamashita and K. R.
Dunbar, J. Am. Chem. Soc., 2006, 128, 11358.
4. Y. L. Bai, J. Tao, R. B. Huang and L. S. Zheng, Angew. Chem. Int.
Ed., 2008, 47, 5344.
5. A. A. Trifonov, I. D. Gudilenkov, G. K. Fukin, A. V. Cherkasov and
J. Larionova, Organometallics, 2009, 28, 3421.
6. H. Miyasaka, N. Motokawa, S. Matsunaga, M. Yamashita, K.
Sugimoto, T. Mori, N. Toyota and K. R. Dunbar, J. Am. Chem. Soc.,
2010, 132, 1532.
1
1
2
2
3
3
4
4
5
5
6
6
7
2
2
7. N. Lopez, H. Zhao, A. V. Prosvirin, A. Chouai, M. Shatruk and K. R.
Dunbar, Chem. Commun., 2007, 4611.
8. M. C. Grossel, A. J. Duke, D. B. Hibbert, I. K. Lewis, E. A. Seddon,
P. N. Horton and S. C. Weston, Chem. Mater., 2000, 12, 2319.
29. W. R. Hertler, H. D. Hartzler, D. S. Acker and R. E. Benson, J. Am.
Chem. Soc., 1962, 84, 3387.
3
0. L. Ballester, A. M. Gil, A. Gutiérrez, M. F. Perpiñán, M. T. Azcondo,
A. E. Sánchez, U. Amador, J. Campo and F. Palacio, Inorg. Chem.,
1
997, 36, 5291.
31. L. R. Melby, R. J. Harder, W. R. Hertler, W. Mahler, R. E. Benson
and W. E. Mochel, J. Am. Chem. Soc., 1962, 84, 3374.
3
3
3
2. T. A. Hudson and R. Robson, Crystal Growth & Design, 2009, 9,
658.
3. R. A. Heintz, H. H. Zhao, X. Ouyang, G. Grandinetti, J. Cowen and
K. R. Dunbar, Inorg. Chem., 1999, 38, 144.
4. H. Miyasaka, T. Madanbashi, K. Sugimoto, Y. Nakazawa, W.
Wernsdorfer, K.ꢀi. Sugiura, M. Yamashita, C. Coulon and R. Clérac,
Chem. ꢁ Eur. J., 2006, 12, 7028.
1
3
5. S. Triki, L. Ouahab, D. Lorcy and A. Robert, Acta Crystallographica
Section C, 1993, 49, 1189.
3
3
6. A. Lombardo and T. R. Fico, J.Org.Chem., 1979, 44, 209.
7. J. P. Gong, I. Kawakami, V. G. Sergeyev and Y. Osada,
Macromolecules, 1991, 24, 5246.
3
3
4
8. M. Yoshikawa, S. Nakashima and A. Mitsuishi, Journal of Raman
Spectroscopy, 1986, 17, 369.
9. Y. L. Zhang, W. J. Ruan, X. J. Zhao, H. G. Wang and Z. A. Zhu,
Polyhedron, 2003, 22, 1535.
0. J. F. Larrow, E. N. Jacobsen, Y. Gao, Y. Hong, X. Nie and C. M.
Zepp, J. Org. Chem., 1994, 59, 1939.
41. D. Zhang, H. Wang, Y. Chen, L. Zhang, L. Tian, Z. H. Ni and J.
Jiang, Dalton Trans., 2009, 43, 9418.
4
4
2. C.Y. Su. Y. P. Cai, A. W. Xu , B. S. Kang , H. Q. Liu, Y. X. Tong , S.
Jie, Polyhedron, 2001, 20, 657.
3. H. Adams, W. Z. Alsindi, G. M. Davies, M. B. Duriska, T. L. Easun,
H. E. Fenton, J. M. Herrera, M. W. George, K. L. Ronayne, X. Z.
Sun, M. Towrie and M. D. Ward, Dalton Trans., 2006, 1, 39.
4. T. A. Miller, J. C. Jeffery, M. D. Ward, H. Adams, S. J. A. Pope and
S. Faulkner, Dalton Trans., 2004, 10, 1524.
5. G. M. Davies, S. J. A. Pope, H. Adams, S. Faulkner and M. D. Ward,
Inorg. Chem., 2005, 44, 4656.
6. Q. Y. Lv, W. Li, S. Z. Zhan, J. G. Wang, J. Y. Su and A. Ding, J.
Organomet. Chem., 2008, 693, 1155.
4
4
4
4
4
7. H. Chun and I. Bernal, Crystal Growth & Design, 2000, 1, 143.
8. R. Rupp, G. Huttner, P. Kircher, R. Soltek and M. Büchner, Eur. J.
Inorg. Chem., 2000, 2000, 1745.
4
9. K. Sakata, Y. Yamaguchi, X. Shen, M. Hashimoto and A. Tsuge,
Synthesis and Reactivity in Inorganic, MetalꢁOrganic, and Nanoꢁ
Metal Chemistry, 2005, 35, 545.
5
5
0. R. M. Haak, M. Martínez Belmonte, E. C. EscuderoꢀAdán, J. Benetꢀ
Buchholz and A. W. Kleij, Dalton Trans., 2010, 39, 593.
1. J. Gao, J. H. Reibenspies, R. A. Zingaro, F. R. Woolley, A. E.
Martell and A. Clearfield, Inorg. Chem., 2004, 44, 232.
2. M. C. Grossel and S. C. Weston, Chem. Mater., 1996, 8, 977.
3. G. Long and R. D. Willett, Inorg. Chim. Acta, 2001, 313, 1.
5
5
6
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Synthesis and Characterization of Cobalt(Ш) Cyanide
Complexes: Cobalt Participate in the Decomposition of Radical
Anion of TCNQ
a,b
a,b
a,b
a,b
a
ChunꢀHong Tan , Xiao Ma , QiꢀLong Zhu , YiꢀHui Huang , YueꢀHong Wen , ShengꢀMin
a
a,
Hu , TianꢀLu Sheng * and XinꢀTao Wu
a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter,
Chinese Academy of Science, Fuzhou, Fujian, 350002 China
b
Graduate University of the Chinese Academy of Sciences, Beijing 100039, China
●
Corresponding author. E-mail: tsheng@fjirsm.ac.cn
A racemic and two chiral cobalt(Ш) cyanide complexes were synthesized by the in situ
decomposition of the radical anion of TCNQ with the participation of cobalt(II)