Self-assembly properties of Salamo-type trinuclear Cu(II) and Co(II) complexes based on the regulation of H+/OHˉ

Article abstract of DOI:10.1002/aoc.4373

A novel naphthalenediol-based bis(salamo)-type tetraoxime compound (H₄L) was designed and synthesized. Two new supramolecular complexes, [Cu₃(L)(μ-OAc)₂] and [Co₃(L)(μ-OAc)₂(MeOH)₂]·4CHCl₃ were synthesized by the reaction of H₄L with Cu(II) acetate dihydrate and Co(II) acetate dihydrate, respectively, and were characterized by elemental analyses and X-ray crystallography. In the Cu(II) complex, Cu1 and Cu2 atoms located in the N₂O₂ sites, and are both penta-coordinated, and Cu3 atom is also penta-coordinated by five oxygen atoms. All the three Cu(II) atoms have geometries of slightly distorted tetragonal pyramid. In the Co(II) complex, Co1 and Co3 atoms located in the N₂O₂ sites, and are both penta-coordinated with geometries of slightly distorted triangular bipyramid and distorted tetragonal pyramid, respectively, while Co2 atom is hexa-coordinated by six oxygen atoms with a geometry of slightly distorted octahedron. These self-assembling complexes form different dimensional supramolecular structures through inter- and intra-molecular hydrogen bonds. The coordination bond cleavages of the two complexes have occurred upon the addition of the H⁺, and have reformed again via the neutralization effect of the OH^?. The changes of the two complexes response to the H⁺/OH^? have observed in the UV–Vis and ¹H NMR spectra.

Full text of DOI:10.1002/aoc.4373

Received: 4 January 2018
DOI: 10.1002/aoc.4373
Revised: 27 February 2018
Accepted: 2 March 2018
F U L L P A P E R
Self‐assembly properties of Salamo‐type trinuclear Cu(II)
and Co(II) complexes based on the regulation of H+/OHˉ
Xiu‐Yan Dong | Bao‐Jun Wang | Quan‐Peng Kang | Wen‐Kui Dong
School of Chemical and Biological
A novel naphthalenediol‐based bis(salamo)‐type tetraoxime compound (H4L)
Engineering, Lanzhou Jiaotong
University, Lanzhou 730070, Gansu,
was designed and synthesized. Two new supramolecular complexes, [Cu3(L)
China
(μ‐OAc)2] and [Co3(L)(μ‐OAc)2(MeOH)2]·4CHCl3 were synthesized by the
reaction of H4L with Cu(II) acetate dihydrate and Co(II) acetate dihydrate,
respectively, and were characterized by elemental analyses and X‐ray crystal-
lography. In the Cu(II) complex, Cu1 and Cu2 atoms located in the N2O2 sites,
and are both penta‐coordinated, and Cu3 atom is also penta‐coordinated by
five oxygen atoms. All the three Cu(II) atoms have geometries of slightly
distorted tetragonal pyramid. In the Co(II) complex, Co1 and Co3 atoms
located in the N2O2 sites, and are both penta‐coordinated with geometries of
slightly distorted triangular bipyramid and distorted tetragonal pyramid,
respectively, while Co2 atom is hexa‐coordinated by six oxygen atoms with a
geometry of slightly distorted octahedron. These self‐assembling complexes
form different dimensional supramolecular structures through inter‐ and
intra‐molecular hydrogen bonds. The coordination bond cleavages of the two
complexes have occurred upon the addition of the H+, and have reformed
again via the neutralization effect of the OH−. The changes of the two com-
Correspondence
Wen‐Kui Dong, School of Chemical and
Biological Engineering, Lanzhou Jiaotong
University, Lanzhou 730070, China.
Email: dongwk@126.com
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 21761018;
Program for Excellent Team of Scientific
Research in Lanzhou Jiaotong University,
Grant/Award Number: 201706
plexes response to the H+/OH− have observed in the UV–Vis and H NMR
1
spectra.
KEYWORDS
crystal structure, Cu(II) and Co(II) complex, response to H+/OHˉ, synthesis
1 | INTRODUCTION
fields, especially in the exploring of molecular antibacte-
rial[50,51] and antitumor medicines.[52]
According to the relevant reports, the Salen‐type ligands
and their corresponding analogues are multifunctional
and important compounds,[1–7] mainly because they are
capable of catalyzing various reactions. Its attractive
properties are used to catalyze,[8–12] luminescence proper-
ties,[13–20] nonlinear optical materials[21] and magnetic
materials,[22–27] supramolecular structures,[28–42] electro-
chemical behaviors[43,44] and biological fields.[45–49] Tran-
sition metal Salen‐type complexes were extensively used
in the application researches of daily life and industrial
Recently, a preferred type of Salen‐type bisoxime
compounds (Salamo and its derivatives) having N2O2
coordination spheres have been reported,[53] which
makes the compounds more stable. The study of
salamo‐type compounds has been well applied.[54–58] In
this article, we have designed and synthesized a
naphthalenediol‐based
bis(salamo)‐type
tetraoxime
compound (H4L) containing two arms of O‐alkyloxime
unit R–CH=N–O–(CH2)n–O–N=CH–R,[59–63] which can
form homotrinuclear transition metal complexes,
Appl Organometal Chem. 2018;e4373.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
1 of 10
https://doi.org/10.1002/aoc.4373

2 of 10
DONG ET AL.
FIGURE 1 (a) View of the molecular
structure of the Cu(II) complex (b)
Coordination polyhedra for Cu(II) atoms
of the Cu(II) complex
FIGURE 2 (a) View of the molecular
structure of the Co(II) complex (b)
Coordination polyhedra for Co(II) atoms
of the Co(II) complex

DONG ET AL.
3 of 10
[Cu3(L)(μ‐OAc)2] and [Co3(L)(μ‐OAc)2(MeOH)2]·4CHCl3.
Further we studied the response of the two complexes
to H+/OHˉ in UV–Vis and 1H NMR spectra,
respectively.
Both the two complexes crystallize in the monoclinic
system, space group P‐1. In the Cu(II) complex, Cu1
and Cu2 atoms located in the N2O2 sites, and are both
penta‐coordinated with geometries of slightly distorted
tetragonal pyramid, and Cu3 atom is also penta‐coordi-
nated by five oxygen atoms with a geometry of slightly
distorted tetragonal pyramid, which were deduced by
calculating the values of τ1 = 0.3033, τ2 = 0.186 and
τ3 = 0.025, respectively. The two μ‐OAc− groups have
connected Cu1 and Cu2 atoms with Cu3 atom act as
‘bridges’. The coordination effect between the (L)4− unit
and the Cu(II) atoms forms a stable chelating complex
[Cu3(L)(μ‐OAc)2], results in the enhancement of the
inflexibility and the formation of two perpendicularly
crossing planes. In the Co(II) complex, Co1 and Co3
atoms located in the N2O2 sites, and are both penta‐
coordinated with geometries of slightly distorted trian-
gular bipyramid and distorted tetragonal pyramid,
respectively. While Co2 atom is hexa‐coordinated by
six oxygen atoms, and has a slightly distorted octahedral
2 | RESULTS AND DISCUSSION
2.1 | Crystal structures of the Cu(II) and
Co(II) complexes.
From a 1:3 mixture of H4L and Cu(II) or Co(II) acetate, a
clear dark blue crystalline Cu(II) complex or a clear dark
reddish brown crystalline Co(II) complex was isolated.
The crystal structures were determined by X‐ray single
crystal diffractions. The crystal structures and atom num-
berings of the Cu(II) and Co(II) complexes are shown in
Figure 1 and Figure 2, selected bond lengths and angles
of the Cu(II) and Co(II) complexes are listed in Table S1
and Table S2, respectively.
FIGURE 3 (a) View of intra‐molecular hydrogen bond and π···π interactions; (b) 2D view of inter‐molecular hydrogen bonds

4 of 10
DONG ET AL.
geometry. Which were deduced by calculating the
values of τ1 = 0.822, τ2 = 0.147 and τ3 = 0.247, respec-
tively. The two μ‐OAc− groups have connected Co1 and
Co2 atoms with Co3 atom act as ‘bridges’. The coordi-
nation effect between the (L)4− unit and the Co(II)
atoms forms a stable chelating complex [Co3(L)(μ‐
OAc)2(MeOH)2]·4CHCl3, while two methanol molecules
bond to the Co3 atom, which results in the
enhancement of the inflexibility and the formation of
two perpendicularly crossing planes.
We studied the inter‐ and intra‐molecular interac-
tions of the two complexes, the Cu(II) complex is linked
by two pairs of inter‐molecular hydrogen bonding inter-
actions form an infinite 2D supramolecular chain. How-
ever, an infinite 1D supramolecular chain of the Co(II)
complex is formed through five pairs of inte‐rmolecular
hydrogen bonding interactions. Hydrogen bonding inter-
actions [Å °] for the Cu(II) and Co(II) complexes are
shown in Table S3. The details of the supramolecular
interactions in the Cu(II) complex are shown in
Figure 3. One intra‐molecular hydrogen bond and π···π
interactions exist between the two aromatic rings (Cg1
(C1‐C6) and Cg2 (C25‐C30)) of the salicylaldehyde in
the Cu(II) complex are shown in Figure 3a.[64] In addi-
tion, two inter‐molecular hydrogen bonds connect two
adjacent molecules (Figure 3b). A long chain has formed
by the Cu(II) complex molecules via inter‐molecular
hydrogen bond interactions, while adjacent chains stack
FIGURE
4
(a) View of intra‐molecular hydrogen bond
interactions; (b) View of 1D inter‐molecular hydrogen bond
interactions; (c) 3D supramolecular structure; (d) 3D model of
structure
FIGURE 5 Spectroscopic titrations of H4L towards (a) Cu2+ and
(b) Co2+

DONG ET AL.
5 of 10
in an interlaced way via Vander Waals force, and result
in a regular array structure. It has a possible application
in the research of molecular wires.
bonds between the ligand and the Cu(II) or Co(II) ions
have formed. The original hydrogen bonding interactions
of the ligand have been destroyed, which leads to the
change of UV–Vis spectra.
The details of the supramolecular interactions in the
Co(II) complex are shown in Figure 4. Intra‐ and inter‐
molecular hydrogen bonds connect two adjacent mole-
cules in the Co(II) complex (Figure 4a and 4b), resulting
in the packing of molecules performs as hollow tubular
materials along a particular direction (Figure 4c), and its
3D model is drawn as Figure 4d by a simulation software.
The diagonal length of the cavity shaped by the molecular
chains is 19.39(4) Å, so the metal complex materials are
considered as a mesoporous, and the solvent molecules
in the cavities are easily replaced by other material, which
makes it possible to store materials of suitable size.
Further we studied the response of the two complexes
to H+/OHˉ. As is shown in Figure 6a, with the addition
of 1.0 equiv H+, the UV–vis spectra of the L‐Cu2+ solution
changed. The characteristic peak at 380 nm have decreased
gradually while three new peaks appear at 340, 360 and
378 nm, which are overlapped with the characteristic
peaks of the H4L, and in the back titration experiment,
with the addition of 1.0 equiv OHˉ, the UV–vis spectra of
the mixed solution have changed and almost are over-
lapped with the initial L‐Cu2+ solution. In the response
of the Co(II) complex towards H+/OHˉ, we have observed
the analogous experiment result. The results mentioned
above probably have demonstrated that the coordination
bonds in the two complexes are destroyed by the addition
of H+, while the coordination bonds have regenerated
owning to the acid–base neutralization (Figure 6b).
2.2 | Response to H+/OHˉ
2.2.1 | Spectroscopic titrations.
In order to study the binding properties of H4L toward
Cu2+ and Co2+ in an organic solvent (Chloroform/metha-
nol: 3:2), UV–vis spectral changes of H4L toward various
concentrations of Cu2+ and Co2+ were carried out. The
results of the spectroscopic titrations are shown in
Figure 5. At 340, 360 and 378 nm, three absorption peaks
of H4L were observed, which can be assigned to n‐π* type
transition. Upon increasing concentration of Cu2+, the
absorption peak of H4L changed at 340, 360 and 378 nm,
with the enhancement of the new wide peak at 380 nm,
which can be assigned to the ligand‐to‐metal charge‐trans-
fer transition (LMCT).[65] The coordination of Cu2+ to the
binding sites of N2O2 and hydroxyl oxygen of the naphtha-
lene ring breaks the intra‐molecular hydrogen‐bonding
interactions of H4L, and increases the coplanarity of the
conjugated system which causes change in the UV–vis
spectra. In addition, upon the addition of Cu2+, the absor-
bance at 425 nm shows a linear enhancement when the
ratio of Cu2+/H4L is below 3:1, and no longer change when
the ratio reaches 3:1. Above this proportion, the absorption
peak at 378 nm has shifted to 372 nm, assuming 3:1 stoichi-
ometry between Cu2+ and H4L (Figure 5a). The analogous
phenomenon happens to the spectroscopic titrations of
H4L towards Co2+. But different from the addition of
Cu2+, the peaks of H4L at 340, 360 and 378 nm also
decreased while two new wide peaks at 365 and 416 nm
appeared, also the absorption peak at 378 nm has shifted
to 396 nm upon the addition of Co2+ (Figure 5b).
To sum up, the coordination ratio of the ligand to the
Cu(II) or Co(II) ions is 1:3. With the gradual addition of
the Cu(II) or Co(II) ions, the Cu(II) or Co(II) complex with
different absorption peaks has formed. The absorption
peaks of the ligand have changed, and new coordination
FIGURE 6 Responses of the (a) Cu(II) and (b) Co(II) complexes
to H+/OHˉ

6 of 10
DONG ET AL.
FIGURE 7 1H NMR spectrums of H4L before and after the addition of 1.0 equiv H+.
FIGURE 8 1H NMR spectrums of L‐Cu2+ before and after the addition of 1.0 equiv H+.
TABLE 1 Crystal data and structure refinements for the Cu(II) and Co(II) complexes
Complex
Cu(II) complex
Co(II) complex
Empirical formula
C34H26Cl4N4O12Cu3
1015.01
C40H38Cl16N4O14Co3
1542.73
Molecular weight
Temperature (K)
293.60 (10)
0.71073
291.10 (2)
0.71073
Wavelength (Ǻ)
Crystal system
Triclinic
Triclinic
Space group
−P1
−P1
a (Å)
b (Å)
c (Å)
α
11.8888 (9)
12.4643 (12)
14.4606 (13)
82.664 (8)
72.637 (8)
84.036 (7)
2023.6 (3)
2
14.5530 (10)
14.7576 (10)
17.2629 (14)
66.329 (7)
89.893 (6)
70.110 (6)
3153.7 (5)
2
β
γ
V (Å3)
Z
(Continues)

DONG ET AL.
7 of 10
TABLE 1 (Continued)
Complex
Dcalc (g/cm3)
Cu(II) complex
1.666
Co(II) complex
1.625
Absorption coefficient (mm−1
)
1.890
1.515
F (000)
1018.0
1542.0
Crystal size (mm)
θ range for data collection(°)
Index ranges
0.24 × 0.22 × 0.21
3.474 to 26.022
0.26 × 0.24 × 0.22
1.507 to 26.999
−15 ≤ h ≤ 14
−16 ≤ k ≤ 16
−19 ≤ l ≤ 19
−18 ≤ h ≤ 17
−18 ≤ k ≤ 18
−21 ≤ l ≤ 21
Reflections collected/ unique
Completeness(%) (θ)
16832 / 79590 Rint = 0.0651
99.7 (25.24)
24781 /13531 Rint = 0.0076
99.7 (25.24)
Data / restraints/ Parameters
7959/0/516
13531/8/810
a
Final R1 / wR2 indices I > 2σ(I)
R1 /wR2 indices (all data)b
GOF
0.0699/0.1563
0.1336/0.1921
0.992
0.0476/ 0.1556
0.0589/0.1600
1.054
2
2
2 21/2
aR1 = ||Fo| − |Fc||/|Fo|. bwR2 = w (Fo − Fc
)
2/w(Fo
)
.
SCHEME 1 The synthetic route to H4L
2.2.2 | 1H NMR spectroscopy
new proton peaks were observed at 10.69 and
10.85 ppm (Figure 7) and we have inferred that the
addition of H+ forms the conjugated acid of the ligand
H4L, which leads to the probable generation of the
inter‐molecular hydrogen bonds. In addition, by com-
In order to study the influence of the acidification by
1.0 equiv H+, the 1H NMR spectroscopy experiments
were carried. By comparing the 1H NMR spectra of
H4L before and after the addition of 1.0 equiv H+, two
1
paring the H NMR spectra of the Cu(II) complex before

8 of 10
DONG ET AL.
and after the addition of 1.0 equiv H+, the experimental
results are obviously different from the ligand H4L, the
new proton peak appears at 10.71 ppm in the 1H
NMR spectra, which indicates the dissociation has
occurred in L‐Cu2+ part after the addition of 1.0 equiv
H+ (Figure 8). The addition of H+ leads to the obvious
hydroxyl peaks observed in L‐Cu2+, which further indi-
cates that the structure of the Cu(II) complex could be
regulated by H+, the experimental results are in agree-
ment with the UV titration spectra and the crystal
structure.
absorption spectra were recorded on a Shimadzu UV‐
2550 spectrometer. X‐ray single crystal structure determi-
nations were carried out on a SuperNova Dual Eos (Cu at
zero) four‐circle diffractometer.
4.2 | X‐ray Crystallographic Analyses
The crystallographic data for the Cu(II) and Co(II) com-
plexes are summarized in Table 1. The single crystals of
the Cu(II) and Co(II) complexes were placed on a
SuperNova, Dual (Cu at zero) Eos. diffractometer. The
diffraction data were collected using
a
graphite
monochromated Mo Kα radiation (λ = 0.71073 A) at
294.10(10) and 291.60(10) K, respectively. The two crystal
structures were solved by direct methods using SHELXS‐
2014 and refinements were done against F2 using
SHELXL‐2014[66]. The H atoms were included at the
calculated positions and constrained to ride on their
parent atoms.
3 | CONCLUSIONS
We have designed and synthesized a naphthalenediol‐
based bis(salamo)‐type tetraoxime H4L, and the struc-
tures of the two transition metal(II) complexes have
been determined by X‐ray crystallographic analyses.
The Cu(II) complex investigates a regular 2D array
structure via inter‐molecular hydrogen bond interactions
and Vander Waals force. In the Co(II) complex, the
diagonal length of the cavity shaped by the molecular
chains is 19.39(4) Å, so the metal complex materials
are considered as a mesoporous, which makes it possi-
ble to store materials of suitable size. The experiment
results in spectroscopic titrations have demonstrated
that the stoichiometry between the two transition
metal(II) ions and H4L are 3:1. The coordination bond
cleavages of the two complexes have occurred upon
the addition of H+, and have reformed again via the
neutralization effect of the OH−, the changes of the
two complexes response to the H+/OH− are observed
in the UV–Vis and 1H NMR spectra, as a result, the
two complexes investigate disaggregation and self‐aggre-
gation behavior via the addition of H+/OH−.
4.3 | Synthesis of the ligand H4L
The ligand H4L has been synthesized by 2‐O‐(1‐
ethyloxyamide)oxime‐4,6‐dichlorophenol
and
2,3‐
dihydroxyn‐ aphthalene‐1,4‐dicarbaldehyde according to
the reported papers earlier.[67–70] The method used in the
process named “One‐Pot”, the detail steps and conditions
were submitted in the Scheme 1. A light yellow powder
was obtained after the purification process. Yield, (62.7%)
1
M.p. 183–185 °C. H NMR (400 MHz, CDCl3): 10.57 (s,
2H), 9.08 (s, 2H), 8.46–8.49 (m, 3H), 8.30 (s, 1H), 7.58 (s,
2H), 7.52–7.53 (s, 2H), 7.35–7.38 (s, 4H), 4.54 (s, 8H). Anal.
calc. For C30H24Cl4N4O8 (%): C, 50.72; H, 3.41; N, 7.89.
Found (%): C, 50.89; H, 3.29; N, 7.79.
4.4 | Synthesis of the Cu(II) complex
A methanol solution (3 ml) of Cu(OAc)2·2H2O (6.56 mg,
0.03 mmol) was added dropwise to a chloroform solution
(3 ml) of the ligand H4L (7.06 mg, 0.01 mmol) at room
temperature. The color of the mixed solution immediately
turned blue. The mixture was filtered and the filtrate was
allowed to stand at room temperature for about two
weeks. The solvent was partially evaporated and clear
dark blue prismatic single crystals suitable for X‐ray crys-
tallographic analysis were obtained. Yield, (42.7%) Anal.
calc. For C34H26Cl4N4O12Cu3 (%): C, 40.38; H, 2.60; N,
5.31. Found (%): C, 40.23; H, 2.58; N, 5.52.
4 | EXPERIMENTAL SECTION
4.1 | Materials and methods
3,5‐Dichlorosalicylaldehyde of 98% purity was purchased
from Alfa Aesar and used without further purification.
The other reagents and solvents were analytical grade
reagents from Tianjin Chemical Reagent Factory. All
the metal salts used were acetates of general formula
M(CH3COO)n·xH2O. Melting points were obtained by
the use of a microscopic melting point apparatus made
in Beijing Taike Instrument Limited Company and were
uncorrected. Elemental analyses were performed by using
a GmbH VarioEL V3.00 automatic elemental analysis
4.5 | Synthesis of the Co(II) complex
1
instrument. H NMR spectra were determined by Ger-
A methanol solution (3 ml) of Co(OAc)2·2H2O (6.48 mg,
0.03 mmol) was added dropwise to a chloroform solution
man Bruker AVANCE DRX‐400 spectrometer. UV–Vis

DONG ET AL.
9 of 10
[15] X. Y. Dong, Q. P. Kang, B. X. Jin, W. K. Dong, Z. Naturforsch.
2017, 72, 415.
(3 ml) of the ligand H4L (7.06 mg, 0.01 mmol) at room
temperature. The color of the mixed solution immedi-
ately turned reddish brown. The mixture was filtered
and the filtrate was allowed to stand at room tempera-
ture for about two weeks. The solvent was partially
evaporated and clear dark reddish brown prismatic sin-
gle crystals suitable for X‐ray crystallographic analysis
were obtained. Yield, (45.7%) Anal. calc. For
C40H38Cl16N4O14Co3 (%): C, 40.19; H, 3.24; N, 5.03.
Found (%): C, 40.06; H, 3.18; N, 5.19.
[16] W. K. Dong, P. F. Lan, W. M. Zhou, Y. Zhang, J. Coord. Chem.
2016, 65, 1272.
[17] L. Zhou, P. Y. Cai, Y. Feng, Anal. Chim. Acta 2012, 735, 96.
[18] N. Subrata, H. S. Wang, G. Michael, Dalton Trans. 2011, 40,
2744.
[19] X. Q. Song, P. P. Liu, Y. A. Liu, J. J. Zhou, X. L. Wang, Dalton
Trans. 2016, 45, 8154.
[20] X. Q. Song, Y. K. Lei, X. R. Wang, M. M. Zhao, Y. Q. Peng, G.
Q. Cheng, J. Solid State Chem. 2014, 218, 202.
[21] P. G. Lacroix, Eur. J. Inorg. Chem. 2001, 32, 339.
ACKNOWLEDGEMENTS
[22] B. Wolfgang, W. Birgit, Inorg. Chim. Acta 2009, 362, 2341.
This work was supported by the National Natural Science
Foundation of China (21761018) and the Program for
Excellent Team of Scientific Research in Lanzhou
Jiaotong University (201706), which is gratefully
acknowledged.
[23] X. Q. Song, P. P. Liu, Z. R. Xiao, X. Li, Y. A. Liu, Inorg. Chim.
Acta 2015, 438, 232.
[24] H. Zhang, W. K. Dong, Y. Zhang, S. F. Akogun, Polyhedron
2017, 133, 279.
[25] P. P. Liu, L. Sheng, X. Q. Song, W. Y. Xu, Y. A. Liu, Inorg.
Chim. Acta 2015, 434, 252.
ORCID
[26] X. Q. Song, Q. F. Zheng, L. Wang, W. S. Liu, Luminescence
2012, 25, 328.
Wen‐Kui Dong http://orcid.org/0000-0003-1249-5808
[27] M. A. Siegler, M. Lutz, Cryst. Growth Des. 2009, 9, 1194.
[28] Y. X. Sun, S. T. Zhang, Z. L. Ren, X. Y. Dong, Synth. React.
Inorg. Met.‐Org. Nano‐Met. Chem. 2013, 43, 995.
REFERENCES
[1] Y. X. Sun, L. Xu, T. H. Zhao, S. H. Liu, G. H. Liu, X. T. Dong,
[29] W. K. Dong, X. L. Li, L. Wang, Y. Zhang, Y. J. Ding, Sens. Actu-
ators B 2016, 229, 370.
Synth. React. Inorg. Met.‐Org. Nano‐Met. Chem. 2013, 43, 509.
[2] L. Q. Chai, G. Liu, J. Y. Zhang, J. J. Huang, J. F. Tong, J. Coord.
Chem. 2013, 66, 3926.
[30] W. K. Dong, S. F. Akogun, Y. Zhang, Y. X. Sun, X. Y. Dong,
Sens. Actuators B 2017, 238, 723.
[3] Y. X. Sun, W. K. Dong, L. Wang, L. Zhao, Y. H. Yang, Chin. J.
Inorg. Chem. 2009, 25, 1478.
[31] W. K. Dong, J. C. Ma, L. C. Zhu, Y. X. Sun, S. F. Akogun, Y.
Zhang, Cryst. Growth Des. 2016, 16, 6903.
[4] X. Q. Song, Y. Q. Peng, G. Q. Chen, X. R. Wang, P. P. Liu,
[32] L. Chen, W. K. Dong, H. Zhang, Y. Zhang, Y. X. Sun, Cryst.
Growth Des. 2017, 17, 3636.
Inorg. Chim. Acta 2015, 427, 13.
[5] C. D. Ene, S. Nastase, C. Maxim, A. M. Madalan, F. Tuna, M.
[33] W. K. Dong, J. C. Ma, L. C. Zhu, Y. Zhang, New J. Chem. 2016,
40, 6998.
Andruh, Inorg. Chim. Acta 2010, 363, 4247.
[6] H. L. Wu, H. Wang, X. L. Wang, G. L. Pan, F. R. Shi, Y. H.
[34] Y. X. Sun, X. H. Gao, Synth. React. Inorg. Met.‐Org, Nano‐Met.
Chem. 2011, 41, 973.
Zhang, Y. C. Bai, J. Kong, New J. Chem. 2014, 38, 1052.
[7] H. L. Wu, G. L. Pan, Y. C. Bai, Y. H. Zhang, H. Wang, F. R. Shi,
[35] Y. H. Yang, J. Hao, Y. J. Dong, G. Wang, W. K. Dong, Chin. J.
Inorg. Chem. 2017, 33, 1280.
X. L. Wang, J. Kong, J. Photochem. Photobiol. B 2014, 135, 33.
[8] R. M. Haak, A. Decortes, E. C. EscuderoAdán, M. M. Belmonte,
E. Martin, J. B. Buchholz, A. W. Kleij, Inorg. Chem. 2011, 50,
7934.
[36] G. Li, J. Hao, L. Z. Liu, W. M. Zhou, W. K. Dong, Crystals 2017,
7, 217.
[37] L. Q. Chai, G. Wang, Y. X. Sun, W. K. Dong, L. Zhao, X. H.
[9] X. Y. Dong, X. Y. Li, L. Z. Liu, H. Zhang, Y. J. Ding, W. K.
Gao, J. Coord. Chem. 2012, 65, 1621.
Dong, RSC Adv. 2017, 7, 48394.
[38] L. Zhao, X. T. Dang, Q. Chen, J. X. Zhao, L. Wang, Synth. React.
Inorg. Met.‐Org. Nano‐Met. Chem. 2013, 43, 1241.
[10] D. J. Darensbourg, Chem. Rev. 2007, 107, 2388.
[11] H. L. Wu, G. L. Pan, Y. C. Bai, H. Wang, J. Kong, F. R. Shi, Y.
[39] L. Zhao, L. Wang, Y. X. Sun, W. K. Dong, X. L. Tang, X.
H. Gao, Synth. React. Inorg. Met.‐Org. Nano‐Met. Chem.
2012, 42, 1303.
H. Zhang, X. L. Wang, J. Chem. Res. 2014, 38, 211.
[12] G. N. Schrauzer, Angew. Chem. Int. Ed. 1976, 15, 417.
[13] W. K. Dong, J. C. Ma, Y. J. Dong, L. C. Zhu, Y. Zhang, Polyhe-
dron 2016, 115, 228.
[40] L. Wang, J. C. Ma, W. K. Dong, L. C. Zhu, Y. Zhang, Z. Anorg,
Allg. Chem. 2016, 642, 834.
[14] L. Xu, L. C. Zhu, J. C. Ma, Y. Zhang, J. Zhang, W. K. Dong, Z.
Anorg. Allg. Chem. 2015, 641, 2520.
[41] P. Wang, L. Zhao, Synth. React. Inorg. Met.‐Org Nano‐Met.
Chem. 2016, 46, 1095.

10 of 10
DONG ET AL.
[42] X. Y. Dong, Y. X. Sun, L. Wang, L. Li, J. Chem. Res. 2012,
36, 387.
[62] X. Y. Dong, S. F. Akogun, W. M. Zhou, W. K. Dong, J. Chinese
Chem. Soc. 2017, 64, 412.
[63] S. Akine, T. Taniguchi, W. K. Dong, S. Masubuchi, T.
[43] S. Akine, T. Taniguchi, T. Nabeshima, Chem. Lett. 2001, 30,
Nabeshima, J. Org. Chem. 2005, 70, 1704.
682.
[64] P. Wang, L. Zhao, Spectrochim. Acta. A 2015, 135, 342.
[44] W. K. Dong, J. C. Ma, L. C. Zhu, Y. Zhang, X. L. Li, Inorg.
Chim. Acta 2016, 445, 140.
[65] T. Ghosh, B. Mondal, T. Ghosh, M. Sutradhar, G. Mukherjee,
M. G. B. Drew, Inorg. Chim. Acta 2007, 360, 1753.
[45] H. L. Wu, Y. C. Bai, Y. H. Zhang, Z. Li, M. C. Wu, C. Y. Chen, J.
W. Zhang, J. Coord. Chem. 2014, 67, 3054.
[66] G. M. Sheldrick, Acta Cryst. A 2008, 64, 112.
[46] H. L. Wu, G. L. Pan, Y. C. Bai, H. Wang, J. Kong, F. R. Shi, Y.
[67] A. J. Gallant, M. Yun, M. Sauer, C. S. Yeung, M. J. MacLachlan,
H. Zhang, X. L. Wang, Res. Chem. Intermed. 2015, 41, 3375.
Org. Lett. 2005, 7, 4827.
[68] S. Sairenji, S. Akine, T. Nabeshima, Tetrahedron Lett. 2014, 55,
[47] H. L. Wu, C. P. Wang, F. Wang, H. P. Peng, H. Zhang, Y. C.
1987.
Bai, J. Chinese Chem. Soc. 2015, 62, 1028.
[69] S. Akine, S. Sairenji, T. Taniguchi, T. Nabeshima, J. Am. Chem.
Soc. 2013, 135, 12948.
[48] C. Y. Chen, J. W. Zhang, Y. H. Zhang, Z. H. Yang, H. L. Wu, G.
L. Pan, Y. C. Bai, J. Coord. Chem. 2015, 68, 1054.
[70] H. A. Tran, J. Collins, P. E. Georghiou, New J. Chem. 2008,
32, 1175.
[49] H. L. Wu, Y. C. Bai, Y. H. Zhang, G. L. Pan, J. Kong, F. R. Shi,
X. L. Wang, Z. Anorg. Allg. Chem. 2014, 640, 2062.
[50] S. M. Mambaa, A. K. Mishraa, B. B. Mambaa, P. B.
Njobehb, M. F. Duttonb, E. Fosso‐Kankeuc, Spectrochim
Acta A 2010, 77, 579.
SUPPORTING INFORMATION
Additional Supporting Information may be found online
in the supporting information tab for this article.
[51] C. Ghosh, G. B. Manjunath, P. Akkapeddi, J. Med. Chem. 2014,
57, 1428.
[52] K. Haranaka, N. Satomi, A. Sakurai, R. Haranaka, N. Okada,
Crystallographic data have been deposited with the
Cambridge Crystallographic Data Centre as supplemen-
tary publication, No. CCDC 1549320 and 1549321 for
the Cu(II) and Co(II) complexes. Copies of the data can
be obtained free of charge on application to CCDC, 12
Union Road, Cambridge CB21EZ, UK (Telephone:
(44) 01223 762910; Fax: +44–1223‐336033; E‐mail:
deposit@ccdc.cam.ac.uk). These data can be also
obtained free of charge at www.ccdc.cam.Ac.uk/conts/
retrieving.html.
M. Kobayashi, Cancer Immunol Immunother 1985, 20, 1.
[53] J. C. Ma, X. Y. Dong, W. K. Dong, Y. Zhang, L. C. Zhu, J. T.
Zhang, J. Coord. Chem. 2016, 69, 149.
[54] Y. J. Dong, J. C. Ma, L. C. Zhu, W. K. Dong, Y. Zhang, J. Coord.
Chem. 2017, 70, 103.
[55] J. Hao, L. L. Li, J. T. Zhang, S. F. Akogun, L. Wang, W. K.
Dong, Polyhedron 2017, 134, 1.
[56] L. Gao, F. Wang, Q. Zhao, Y. Zhang, W. K. Dong, Polyhedron
2018, 139, 7.
[57] S. Akine, T. Nabeshima, Dalton Trans. 2009, 47, 10395.
[58] L. Wang, X. Y. Li, Q. Zhao, L. H. Li, W. K. Dong, RSC Adv.
2017, 7, 48730.
How to cite this article: Dong X‐Y, Wang B‐J,
Kang Q‐P, Dong W‐K. Self‐assembly properties of
Salamo‐type trinuclear Cu(II) and Co(II) complexes
based on the regulation of H+/OHˉ. Appl
Organometal Chem. 2018;e4373. https://doi.org/
10.1002/aoc.4373
[59] W. K. Dong, J. Zhang, Y. Zhang, N. Li, Inorg. Chim. Acta 2016,
444, 95.
[60] L. Q. Chai, K. Y. Zhang, L. J. Tang, J. Y. Zhang, H. S. Zhang,
Polyhedron 2017, 130, 100.
[61] Y. X. Sun, L. Wang, X. Y. Dong, Z. L. Ren, W. S. Meng, Synth.
React. Inorg. Met.‐Org. Nano‐Met. Chem 2013, 43, 599.