Copper complex based on 2-(phenylimino-methyl)-phenol as a high selective fluoresencent probe for hydrogen sulfide

Article abstract of DOI:10.1016/j.poly.2015.11.022

A Copper(II) complex of condensation production was synthesized and its crystal was also obtained by the reaction of 2-(phenylimino-methyl)-phenol with Cu(CH₃COO)₂·H₂O. The crystal and molecular structure of the complex wa

Full text of DOI:10.1016/j.poly.2015.11.022

Accepted Manuscript
Copper complex based on 2-(phenylimino-methyl)-phenol as a high selective
fluoresencent probe for hydrogen sulfide
Kui Ren, Xuefang Shang, Jiajia Fu, Peipei Zhao, Jinlian Zhang
PII:
S0277-5387(15)00699-3
DOI:
http://dx.doi.org/10.1016/j.poly.2015.11.022
POLY 11667
Reference:
Polyhedron
To appear in:
Received Date:
Accepted Date:
12 October 2015
15 November 2015
Please cite this article as: K. Ren, X. Shang, J. Fu, P. Zhao, J. Zhang, Copper complex based on 2-(phenylimino-
methyl)-phenol as a high selective fluoresencent probe for hydrogen sulfide, Polyhedron (2015), doi: http://
dx.doi.org/10.1016/j.poly.2015.11.022
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Copper complex based on 2-(phenylimino-methyl)-phenol as a
high selective fluoresencent probe for hydrogen sulfide
Kui Rena, Xuefang Shanga*, Jiajia Fub, Peipei Zhaob, Jinlian Zhangb
aDepartment of Chemistry, Xinxiang Medical University, Xinxiang, Henan 453003, China
bSchool of Pharmacy, Xinxiang Medical University, Xinxiang, Henan 453003, China
*Corresponding author: Tel +86-373-3029128, Fax +86-373-3029959
E-mail: xuefangshang@126.com
Abstract:
A Copper(II) complex of condensation production was synthesized and its crystal
was also obtained by the reaction of 2-(phenylimino-methyl)-phenol with
Cu(CH3COO)2·H2O. The crystal and molecular structure of the complex was
determined by single-crystal X-ray diffraction, IR, and HRMS. The Cu(II) ion was
four coordinated with two phenolate oxygen and two imine nitrogen atoms in a
square-planar geometry. It should be emphasized that the complex demonstrated high
−
−
−
selectivity and sensitivity for hydrogen sulfide over other anions (AcO , H2PO4 , F , Cl
−
−
−
, Br and I ) followed by the release of copper ion to give a remarkable increase of
fluorescence intensity in various organic-aqueous solutions. The synthesized copper
complex could be used as a fluoresencent probe for the detection of HS- in the sample
of environment, pharmacy, and etc.
Key words: hydrogen sulfide; fluoresencent probe; copper complex crystal
1. Introduction
Hydrogen sulfide (H2S), which is believed to have been critical to the origin of life
on earth, was considered merely as a toxin with no beneficial physiological
significance until the initial observations by Kimura’s group suggesting its biological
1

relevance as a signaling molecule [1]. Now hydrogen sulfide( H2S) is considered to be
the third member of the gasotransmitter family along with carbon monoxide(CO) and
nitric oxide(NO) [2-6]. H2S appears to be involved in various physiological processes,
including relaxation of vascular smooth muscles, mediation of neurotransmission,
regulation of inflammation and O2 sensing, and it can also protect against
ischemia/reperfusion injury [7-11]. On the other hand, disruption of the H2S level is
linked to some diseases such as Alzheimer’s disease, Down’s syndrome, diabetes and
liver cirrhosis [12-16]. For any study of its biological functions, it is important to take
the concentration at the first consideration. Therefore, the selective recognition and
detection of H2S is very significant for the better understanding on physiological and
pathological function and has become the important subject of chemical research. So
far, a variety of detection methods including colorimetric, electrochemical,
chemoluminescence, chromatography, and methylene blue assay[16-21] have been
developed for the detection of H2S. There are generally limited by their invasive and
destructive nature to the living organisms. On the other hand, small fluorescent probes
have attracted the most attention for sensing and visualizing analytes in living cells
because of their high sensitivity, good cell permeability and high water solubility
[22-27]. This technology may provide a real-time, easy-to-use, nondestructive
detection method in live cells or tissues [28-35]. Based on the H2S-triggered specific
reactions, such as Cu2+ quencher removal [36], reduction of azide [37], nucleophilic
reaction [38], a few small molecular fluorescent turn-on probes [39-40] and
ratiometric probes [41-42] have been successfully developed for H2S, and some of
them could even been used for intracellular H2S imaging [43-44].
Based on the above considerations, we synthesized a copper(Ⅱ) complex (scheme
1) to research the anion binding ability, especially for HS-. Fortunately, the crystal of
2

the copper complex was also obtained and showed suitable water solubility. As
expected, the complex displayed the strongest binding ability for HS- among the
-
−
−
−
−
−
−
tested anions (HS , AcO , H2PO4 , F , Cl , Br and I ).
Scheme 1 Synthesis route for copper(Ⅱ) complex
2. Material and methods
All reagents and solvents used were of analytical grade. Sodium hydrosulfide
hydrate, all anions in the form of tetrabutylammonium salts (such as (n-C4H9)4NCl,
(n-C4H9)4NBr, (n-C4H9)4NI, (n-C4H9)4NAcO and (n-C4H9)4NH2PO4) were purchased
from Aladdin Chemistry Co. Ltd (Shanghai, China). All anions were stored in a
desiccator under vacuum, and used without any further purification. Dimethyl
1
sulfoxide (DMSO) was distilled in vacuum after being dried with CaH2. H NMR
spectra were recorded on a Unity Plus-400-MHz spectrometer. HRMS was performed
with a Mariner apparatus. UV-vis titration experiments were made on a Shimadzu
UV2550 Spectrophotometer (Shimadzu, Japan) at 298 K. Fluorometric titration was
performed on a Cary Eclipse Fluorescence Spectrophotometer (Agilent, USA) at 298
K. The binding constant, Ks, was obtained by non-linear least squares calculation
method for data fitting.
The copper complex was synthesized according to the route shown in Scheme 1.
The condensation product between salicylaldehyde and phenylamine was
synthesized according to the literature [45]. The ethanol solution (40 mL) containing
salicylaldehyde (10 mmol) and phenylamine (10 mmol) was refluxed for 4 h and the
yellow precipitate was recrystalled by ethanol-water (1:1, v:v), washed with water,
3

and dried under vacuum. Yield: 85%. m.p. 46-48℃. IR (KBr pellet, cm-1): 3446
(-OH), 1616(-CH=N), 1280(-C-O). 1H NMR (400 MHz, DMSO) ꢀ 13.10 (s, 1H, -OH),
8.97(s, 1H, -CH=N-), 7.67 (dd, 1H, ph-H), 7.45 (dtd, 5H, ph-H), 7.32(m, 1H, ph-H),
6.99 (m, 2H, ph-H). Elemental analysis: Calc. for C13H11NO: C, 79.16; H, 5.62; N,
7.10; Found: C, 79.53; H, 5.94; N, 7.02. ESI-MS (m/z): 196.1 (M-H)-.
Synthesis of Cu(Ⅱ) complex
It was synthesized according to the literature [46]. The condensation product (242
mg, 1 mmol) between salicylaldehyde and phenylamine was resolved in ethanol (15
mL). After the copper acetate hydrate (99 mg, 0.5 mmol) was added to the above
solution, the mixture was stirred for 1 h at 55 and then stood overnight at room
temperature. Suitable brown single crystal for X-ray structural analysis was obtained,
separated by filtration, washed with petroleum ether. Yield: 80%. m.p. 239-242℃.
Elemental analysis: Calc. for C26H18CuN4O6: C, 68.48; H, 4.42; N, 6.14; Found: C,
68.73; H, 4.72; N, 6.02. IR (KBr pellet, cm-1): 1606(-CH=N), 1317(-C-O),
545(-Cu-O), 418(-Cu-N). ESI-HRMS (m/z): 478.0703 (M+Na)+.
3. Results and discussion
3.1 X-ray crystal structure
Single crystal X-ray analysis was used to determine the structure of the copper
complex. An ORTEP view of the copper complex with the atoms number was shown
in Fig. 1. A detailed crystal data, data collection and refinement details were given
in Table 1. Selected bond lengths and bond angles were listed in Table 2. Compared
with the previous four-coordinated copper complex [47-50], all bond lengths and
angles were within the normal ranges. The crystallographic data revealed that the
metal center was four-coordinated by two oxygen atoms and two imine nitrogen
atoms in two Schiff base ligands. The ligand was coordinated to the Cu(II) center
4

in trans- orientation with respect to each other. The length of Cu-O bond was shorter
than that of Cu-N bond. The geometry around the metal center was a distorted
square-planar, with P21/c space group. The cell dimensions and space group of the
same complex have been reported by Stogsdill, Kamenar and Jian Fangfang [51-53].
There were also five-coordinated complexes with the central copper atom which
adopted a distorted square pyramidal geometry [54] and six-coordinated complexes
which formed octahedron geometry with copper atom in the center [55]. Tridentate
ligand or tetradentate ligand was involved in the formation of the complexes. To the
best of our knowledge, most of bidentate ligands was organized four-coordinated
complex as the mentioned above [56].
Fig.1 The molecular structure of copper complex
5

Table 1. Crystallographic and experimental data for the Cu(Ⅱ) Complex
Empirical formula
Formula weight
Temperature
C26H20CuN2O2
455.98
296(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P 21/n
Unit cell dimensions
a = 11.9215(11) Å
b = 7.9662(8) Å
c = 12.1770(12) Å
α= 90°
β= 112.269(3)°
γ = 90°
3
Volume
Z
1070.19(18) Å
2
3
Density (calculated)
1.415 Mg/m
-1
Absorption coefficient
F(000)
1.046 mm
470
3
Crystal size
Theta range for data collection
Index ranges
Reflections collected
Independent reflections
Completeness to theta = 25.242°
Absorption correction
Max. and min. transmission
0.503 x 0.498 x 0.058 mm
3.132 to 27.514°.
-15<=h<=15, -10<=k<=10, -15<=l<=15
13644
2460 [R(int) = 0.0895]
99.9 %
Semi-empirical from equivalents
0.941 and 0.597
2
Refinement method
Full-matrix least-squares on F
Data / restraints / parameters
2460 / 0 / 142
2
Goodness-of-fit on F
1.074
Final R indices [I>2sigma(I)]
R indices (all data)
Extinction coefficient
R1 = 0.0576, wR2 = 0.1975
R1 = 0.0801, wR2 = 0.2442
n/a
-3
Largest diff. peak and hole
0.527 and -0.774 e.Å
Table 2. Selected bond lengths (Å) and angles (°) for the complex
Cu(1)-O(1)
1.883(3)
Cu(1)-O(1)#1
1.883(3)
Cu(1)-N(1)
Cu(1)-N(1)#1
2.002(3)
180.0
2.002(3)
180.0
O(1)#1-Cu(1)-O(1)
O(1)#1-Cu(1)-N(1)
O(1)-Cu(1)-N(1)
N(1)-Cu(1)-N(1)#1
O(1)-Cu(1)-N(1)#1
O(1)#1-Cu(1)-N(1)#1
88.58(12)
88.58(12)
91.42(12)
91.42(12)
Symmetry transformations used to generate equivalent atoms: #1 -x+2,-y,-z+2
3.2 UV-vis titration
The binding ability of copper complex with various anions was investigated using
UV-vis absorption spectra in DMSO-H2O (9:1, v/v) at 298 K. The UV-vis spectral
changes of copper complex were shown in Fig. 2 during the titration with NaHS. The
6

absorption band of Cu(Ⅱ) complex (8.0×10−5 molꢁL-1 in DMSO) centered at 384 nm
was gradually decreased and shifted to the blue wavelength direction (at 336 nm).
Four clear isosbestic points at 261, 273, 303 and 366 nm appeared which indicated the
stable complex formed having a certain stoichiometric ratio between the Cu(Ⅱ)
complex and HS-. Analogous investigations were carried out on other normal anions.
-
The additions of H2PO4 , AcO- and F- to Cu(Ⅱ) complex induced similar spectral
changes (Fig. 2) which indicated Cu(Ⅱ) complex also interacted with the above
anions. However, the additions of Cl- , Br- and I -did not induce any spectral responses.
The above results indicated that Cu(Ⅱ) complex showed almost no binding ability
toward these anions.
HS-
AcO-
-
F-
H2PO4
Fig. 2 UV-vis spectral changes of Cu(Ⅱ) complex upon the addition of various anions.
[complex] = 8.0×10-5 mol·L-1 in DMSO-H2O (9:1, v/v). Arrows indicate the direction
of increasing anions concentration.
7

3.3 Fluorescent response
The fluorescence properties of the Cu( ) complex was also investigated in DMSO
and DMSO-H2O (1:1, v/v). The free probe displayed weak fluorescence intensity
upon excitation at 390 nm. As shown in Fig. 3, the fluorescence emission intensity
was gradually strengthened at about 490 nm with the increasing concentration of HS-.
The interacted process completed within 20 min and very quick. The reason may be
that the addition of HS- could coordinate with Cu2+ and release the free ligand. In
order to test the real-world applicability of the probe, we conducted the HS- recovery
rate of the probe in tap water. A 15-fold fluorescence enhancement suggested that the
probe could be a good candidate for the detection of HS- in tap water (Fig. 3). The
fluorescence titration of the probe with various anions was conducted to examine the
−
selectivity. As shown in Fig. 4(a), the addition of 100 equiv. of AcO−, H2PO4 , F−, Cl−,
Br− and I− produced a nominal change in the fluorescence spectra of the probe. All
these results suggested that the complex probe was a practical probe for detection of
HS- with high selectivity. The pH work range test was shown in Fig. 4(b), there was
almost no spectral change of the free complex probe at 500 nm in a range of acidic
media. However, when the pH value was increased from neutral to basic the
fluorescence intensity was increased significantly. Interestingly, distinct fluorescence
changes were obtained in the presence of NaHS at pH 5-7. Additionally, the complex
was stable enough as a probe because no obvious changes in the absorption spectrum.
Fluorescence intensity was observed after the solution of complex crystal was stored
at room temperature for a month.
8

c
b
a
Fig. 3 Fluorescence response (ꢂex, 390nm) of copper probe (8.0×10−5 molꢁL-1) upon
the addition of NaHS. Arrows indicate the increase direction of NaHS concentration.
All the spectra were acquired after reaction of the probe with NaHS for 20 min. (a)
NaHS (0 - 2.0×10−3 molꢁL-1), in DMSO; (b) NaHS (0 - 8.0×10−4 molꢁL-1), in
DMSO-H2O (1:1, v/v, ); (c) NaHS (0 - 4.0×10−4 molꢁL-1), in DMSO-Tap water (1:1,
v/v).
a
b
Fig. 4 (a) Fluorescence spectra (ꢂex, 390 nm, slit widths: 10 nm/10 nm) of probe
(8.0×10−5 molꢁL-1) upon the addition of various anions (20 equiv.) in DMSO; (b)
Plotting the fluorescence intensity (ꢂex, 390nm) of copper probe without NaHS (black)
and with NaHS (2.0×10−3 molꢁL-1) (red) at different pH.
9

3.2 Binding constant
−
Cu(Ⅱ) complex interacted with anions as the ratio of 1:2 except AcO according
to the non-linear fitting curves (Fig. 5). The corresponding coefficients were all
greater than 0.99. The binding constants could be obtained and listed in Table 3 based
on the UV–vis and fluorescence titration data [57-59]. Obviously, the anion binding
−
−
−
−
−
constants of Cu(Ⅱ) complex were in the order: H2PO4 > F >HS > AcO >> Cl ~
-
−
−
Br ~ I . However, only the addition of HS could induce the remarkable spectral
change of copper complex in fluorescence spectra. And the corresponding binding
constants were listed in Table 3, which the values were (5.29 0.08) × 107 in DMSO
and (6.29 0.4)×105 in DMSO-H2O (5:5, v/v), respectively. The probe of Cu(Ⅱ)
complex showed the strongest binding ability for HS- among the anions tested. The
reason may be related to the displacement reaction which the Cu2+ was captured by
HS- and free ligand was released from the complex. The above results indicated the
synthesized copper complex could be used as a fluorescence probe for HS- in the
sample of environment or pharmacy.
a
c
b
e
d
f
Fig. 5 Non-linear fitting curves of Cu( ) complex in DMSO (a) or H2O/DMSO (b,
1:1) or DMSO/H2O (c, 9:1) upon the addition of HS-; DMSO/H2O (d, e, f, 9:1) upon
10

the addition of other anions.
Table 3 Binding constants of Cu(Ⅱ) complex with various anions
Ks(DMSO:H2O
(1:1, v/v)
Ks(DMSO:H2O
(9:1, v/v)
UV-vis data
Ks(DMSO)
anions
HS-
Fluorescence data
(8.3 0.05)×106b
(6.29 0.4)×105b
(5.29 0.08)×107b
-
H2PO4
(6.61 0.05)×108b
ND
ND
F-
AcO-
Br-
Cl-
(1.43 0.01)×108b
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(854 7)c
NDa
ND
I-
ND
aThe binding constant could not be determined
bThe binding ratio of host-guest is 1:2
cThe binding ratio of host-guest is 1:1
3.3 Mechanism
Many literatures had been researched on the anion binding. However, a full
understanding of the principles that govern anion recognition had not yet been
achieved. The most possible mechanism was that other anions could only coordinate
with complex probe to form a six-coordinated complex according to comprehensive
−
analysis of UV-vis and fluorescent titration. The oxygen atom in AcO , “Y” shape
anion, could coordinate with the probe as the ratio of 1:1. But NaHS could snatch the
copper ion from the complex due to the much higher binding constant between sulfide
and copper ion (Scheme 2). The fluorescent responses also could illustrate it. As
shown in Fig. 5, only the addition of HS- could snatch the copper ion and release the
free ligand following with a dramatic increase of the fluorescence intensity. However,
other anions were coordinated to the probe accompanied with a weak fluorescence
response.
11

Scheme 2. The possible binding mode between the copper complex and hydrogen
sulfide ion
4. Conclusion
In conclusion, the results obtained in this study indicated that the copper complex
could be used as a high selective and strong sensitive fluorescent probe for the
detection of H2S. Since our tests were performed in aqueous solutions, we expected
the compound to be a convenient and practical probe for the detection of HS- in
biological samples. The above method has some advantages such as the simplicity
analysis and low cost of the starting material in the present system. The complex
holds great potential for environmental analysis of HS-, S2-, H2S and the application in
bio-analysis is still challenging.
Acknowledgment
This work was supported by the National Natural Science Foundation of China
(81301269) and Program for Science & Technology Innovation Talents in Universities
of Henan Province (15HASTIT039).
Appendix A. Supplementary data
CCDC 1411387 contains the supplementary crystallographic data for the copper
complex reported in this paper. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html,
or
from
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.
12

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A Copper(II) complex crystal based on 2-(phenylimino-methyl)-phenol was
synthesized. The complex demonstrated high selectivity and sensitivity for hydrogen
−
−
−
−
−
−
sulfide over other anions (AcO , H2PO4 , F , Cl , Br and I ) in aqueous solution.
.