1,9-Dicarbonyl-2,8-dioxo-butyne-ester Ferrocenophane: Synthesis, Structure and Recognition Properties for Co2+ and Cu2+ Ions

Article abstract of DOI:10.1134/S1070427217120187

An efficient highly diluted synthetic approach to the synthesis of 1,9-dicarbonyl-2,8-dioxo-butyne ester ferrocenophane (L) has been developed. The title compound was characterized by IR, UV, FL, 1H NMR, spectroscopies, elemental analysis and so on. Furth

Full text of DOI:10.1134/S1070427217120187

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2017, Vol. 90, No. 12, pp. 2016−2018. © Pleiades Publishing, Ltd., 2017.
VARIOUS TECHNOLOGICAL
PROCESSES
1
,9-Dicarbonyl-2,8-dioxo-butyne-ester Ferrocenophane:
Synthesis, Structure and Recognition Properties
2+
2+
1
for Co and Cu Ions
a,
a
a
a
a
b
Xiaoju Liu *, Guoyu Ren , Xiangrong Ma , Yulin Xiang , Liguo Gao , and Xiaoyan Ma
aKey Laboratory of Synthetic and Natural Chemistry of the Ministry of Education, Chemical Engineering Institute,
the Yu-Lin University of Yulin, Chongwen Avenue 4, Yulin 719000, Shaanxi Province, People’s Republic of China
b
Department of Applied Chemistry, School of Natural and Applied Sciences, Northwestern Polytechnical University,
Xi’an, Shaanxi 710129, China
*
e-mail: liuxiaoju0628@163.com
Received December 25, 2017
Abstract—An efficient highly diluted synthetic approach to the synthesis of 1,9-dicarbonyl-2,8-dioxo-butyne
1
ester ferrocenophane (L) has been developed. The title compound was characterized by IR, UV, FL, H NMR,
2
+
2+
spectroscopies, elemental analysis and so on. Further complex L shows fluorescence responses to Co and Cu
in CH OH, The results indicate that the complex could be applied in multianayte detection. The binding ability of
3
2
+
2+
2+
2+
receptor L CH OH was tested for various cations (Co , Cu , Zn , and Ni in water) and the binding constants
3
2
+
2+
for Co and Cu were the computed, having a distinct absorbance shift. The receptor is a very attractive array
because its distinct absorbance shift profile in a semi-aqueous phase, making it applicable in the area of biology,
environmental sciences and material chemistry.
DOI: 10.1134/S1070427217120187
Ferrocene derivatives have been widely utilized in
various fields, mainly owing to their unique structural,
electronic, thermal stability, high nonlinear optical
susceptibility, and magnetic properties [1–3].
(0.0015 mol)] was added dropwise during 6 h to a stirred
mixture of 2-butyne-1,4-diol 0.129 g (0.0015 mol),
1000 mL of dry DCM, and 0.24 mL (0.003 mol) of
pyridine at room temperature. The mixture was stirred
for one day at room temperature and then refluxed for
another 6 h (monitored by thin-layer chromatography,
TLC). About 900 mL of the solvent was evaporated, and
the residual solution was washed with 50 mL of water
In the title novel compound, lone pair electrons of
O atom which on the bridges face to cavity, form a
hydrophilic and rich electronic cavity. They can form
different types host-guest coordination compounds with
appropriate cationic by metal-dipole force, and possibly
the compound will be used as chemical sensor and
simulation enzyme [4, 5]. In this paper, a novel ferrocenyl
heterocyclic compound L were synthesized (Scheme 1)
starting from ferrocene via 1,1'-diacetylferrocene (a),
several times and dried over anhydrous MgSO .After fil-
4
tering the solvent was removed leaving a crude product.
Column chromatography on silica gel (petroleum ether :
ethyl acetate : dichloromethane = 10 : 4 : 1) afforded
ester ferrocenophane. Data for ester ferrocenophanes:
Yellow solid (45%), mp 170–172°C. 1H NMR (CDCl3)
1
,1'-ferrocene-dicarboxylic acid (b), 1,1'-ferrocene-
di(carbonyl chloride) (c) with dihydroxyethyl aniline (d)
under high dilute condition.
δ, ppm: 7.39 (m, 2H, Fc-H), 7.33 (m, 2H, Fc-H), 4.36
(
m, 2H, Fc-H), 4.22(s, 4H, (–O–CH –)), IR (KBr) υ,
2
–
1
cm : 3451, 2951, 2926, 2852, 1731, 1601, 1423, 1386,
1
EXPERIMENT
–
1
189, 1116, 1079, 930, 820, 708, 622, 585 cm . Anal.
1
,9-Dicarbonyl-2,8-dioxo-butyne-ester ferroce-
calcd. of C H FeO ; Calculated: C 59.29; H 3.73;
1
6
12
4
nophane. 1,10-Ferrocene-di(carbonyl chloride) [0.5 g
Found: C 59.32; H 3.70. MALDI-TOP MS m/z =
1
325[M+H] (Scheme 1).
+
The text was submitted by the authors in English.
2
016

1
,9-DICARBONYL-2,8-DIOXO-BUTYNE-ESTER FERROCENOPHANE
2017
Scheme 1.
was recorded in a range of 200–800 nm. The effect of
a broad array of environmentally and physiologically
active metal ions was investigated for receptor L using the
UV–vis spectra of solutions containing this receptor and
RESULTS AND DISCUSSIONS
Sample preparation. A stock solution of receptor L
–
6
(
c = 1 × 10 M) in CH OH was prepared and the solutions
3
a specific metal ion in H O solutions as shown in Fig. 1.
2
–
5
of metal ions (c =1 × 10 M) were simply prepared by
The results show that metal ions such as Zn2+ and Ni2+
diluting with H O. All stock and working solutions were
prepared in ultrapure water and spectroscopic grade
methanol.
2
do not change the absorption peaks of receptor L. The
observed binding behavior of the ligand can be attributed
to the presence of donor atoms that favor the binding with
Co and Cu in a tetrahedral fashion. The availability
of the electron-rich cavity is provided by O atoms of the
ligand, which has an important role in cation binding
alongside a reagent blank.
2
+
2+
UVvisibleanalysis. TheUV-visiblespectrophotometer
experiments were carried out in a CH OH solvent system
3
at room temperatures (298 K) to determine the selectivity
2
+
2+
2+
2+
among the metal ions (Co , Cu , Zn , and Ni in
water) with the receptor/ligand. The absorbance intensity
Fluorescence analysis. The fluorescence intensity
Fig. 1 Absorption spectra of receptor L (c = 1 × 10–6 M) in
Fig. 2. Fluorescence emission spectra of L (CH OH c = 1 ×
3
–6
CH OH solution upon addition of various metal ions (c = 1 ×
10 M) in the absence and presence of various cations (c =
3
5
–
–5
1
0
M) in water.
1 × 10 M) in H O solution. λ = 390 nm.
2
ex
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017

2018
XIAOJU LIU et al.
CONCLUSIONS
In summary, we have synthesized the selective and
sensitive fluorescent chemical sensor ferrocene macro-
2
+
2+
cyclic complex L for the detection of Co and Cu in
CH OH medium. Receptor L could be applied directly for
3
real environmental samples because of its working ability
2+
2+
in semi-aqueous solution. The detection of Co and Cu
gives rise to a major colorimetric color change, which
can be easily detected by the naked eye. Furthermore,
our sensor is not affected by the common interference of
other ions. This plan of nitrogen wealthy little molecules
can provide a standard for the discovery of fluorescent
chemosensors for the detection of multi-metal ions.
Development of other novel fluorescent chemosensors
based on similar ligands is in progress in our laboratory.
2
+
Fig. 3. The type of proposed recognizing mechanism of Co
and Cu with L as a probe.
2
+
was recorded at λ /λ = 390/470 nm alongside a reagent
blank. The excitation and emission slits were both set to
.0 nm. This was followed by a 5 min interval (in which
the reaction cell was left under continuous stirring to
ex em
5
ensure mixing), then the fluorescence data were collected.
ACKNOWLEDGMENTS
Receptor L shows a strong fluorescence emission at
4
70 nm when excited at 390 nm. Upon the addition of
This work was supported by Instrumental Analysis
Zn and Ni fluorescence emission spectra of receptor L Center of the Chemical Engineering Institute, the Yu-Lin
2+
2+
showed no change. However, there is a notable change
University, the Scientific research fund project (grant
no. 2016NY-221), the Key Laboratory Project Foundation
of Shaanxi Provinci al Education Department in China
(17JS144).
2
+
2+
when Co and Cu are present. Figure 2 shows that
2+
2+
when Co + and Cu were added, the fluorescence was
blue shift, which is likely due to the fact that conjugated
system of L was destroyed. The observed changes might
be due to electron transfer in the excited state and the
paramagnetic nature of both cations or due to complex
formation between receptor L and cations, which is
certainly because of coordination of C=O lone pairs with
the metal ions. The reason for the fluorescence change in
receptor L is probably due to the occurrence of either an
electron transfer or an electronic energy transfer involving
the transition metal and the excited fluorophore, as it is
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1
. Vicente, M.C., Burguete, M.I., Galindo, F., Izquierdo, M.A.,
Kumar, D.K., and White,A.J., J. Org. Chem., 2012, vol. 77,
p. 490.
2
3
4
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vol. 15, p. 520.
2
+
2+
observed in other Co and Cu recognition sensors.
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Kanaparthi, R.K., and Sivasankar, C., Org. Lett., 2013,
vol. 15, p. 306.
2
+
We also tried to grow single crystals of both Co
2+
and Cu complexes of receptor L, but unfortunately no
crystals were obtained which were suitable for diffraction
study (Fig. 3).
5. Wei, T.B., Zhang, P., Shi, B.B., Chen, P., Lin, Q., Liu, J.,
and Zhang, Y.M., Dye. Pigm., 2013, vol. 97, p. 297.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 90 No. 12 2017