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Synthesis structural characterization and electrochemical recognition of metal ions of two new ferrocenylhydrazone-based receptors.

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Full Paper
Received: 6 May 2009
Revised: 22 June 2009
Accepted: 29 June 2009
Published online in Wiley Interscience: 14 August 2009
(www.interscience.com) DOI 10.1002/aoc.1535
Synthesis, structural characterization
and electrochemical recognition of metal
ions of two new ferrocenylhydrazone-based
receptors
Chunjie Qiao, Jie Li, Yan Xu∗ , Shuyan Guo, Xue Qi and Yaoting Fan
Two new ferrocenylhydrazone-based receptors FcL1 and FcL2 were prepared and the X-ray crystal structure of FcL1 was
described. The electrochemical studies reveal that the receptor FcL1 is responsive to Hg2+ and Cr3+ , whereas, receptor FcL2
c 2009 John Wiley &
only responsive to Hg2+ . The maximum electrochemical shift of FcL1 for Cr3+ is about 56 mV. Copyright Sons, Ltd.
Supporting information may be found in the online version of this article.
Keywords: synthesis; structural characterization; electrochemical recognition; receptor
Introduction
The design and synthesis of new electrochemically active receptors
for ion selective detection have received considerable attention
in recent years.[1 – 12] Many compounds containing functional
groups, such as pyrrole, urea, sulfonamide and hydrazone, can
act as receptors.[13 – 16] Among these, hydrazone-based receptors
have strong binding ability with ions and are readily available.[17]
Substituents on the functional group affect the properties of
the receptors to some extent. Ferrocene-containing compounds
have their own specialties owing to their special sandwich
structure. In coordination chemistry, when ions attract ligands
forming coordination compounds, the HOMO energy level of the
ligands changes.[18] Therefore, ferrocene/ferrocenium (Fc/Fc+ )
itself represents a strictly reversible one-electron redox couple,
and the redox behavior is influenced by changing energy levels of
the HOMO.[13] Therefore, ferrocene derivatives have been widely
investigated in the field of electrochemistry and possible ionselective sensing applications reviewed.[19 – 26] It is known that
ferrocenyl-bearing hydrazones can form stable complexes with
various transition metal ions.[27,28] However, there has been limited
study about their electrochemical sensing properties. Taking these
into consideration, we synthesized two new ferrocenylhydrazonebased receptors, referred to from now on as FcL1 and FcL2 ,
respectively, reported in Scheme 1. From the electrochemical
study, we found that the new compounds show selective potential
response to some metal ions.
Experimental
Appl. Organometal. Chem. 2009 , 23, 421–424
Mel-Temp IV apparatus and are uncorrected. IR spectra of the receptors were measured on a Perkin-Elmer FTIR-1750 spectrometer
using KBr pellets. Elemental analyses were performed on Flash
1112 elemetal analyzer. 1 H NMR spectra were recorded at room
temperature on a Bruker DPX 400 MHz spectrometer in CDCl3 as
a solvent. Chemical shifts are denoted in δ units (ppm) relative
to Me4 Si as internal standard. UV–vis spectra were recorded on a
Unico UV-2102 PC spectrometer in acetonitrile. Electrochemical
experiments were performed in dry acetonitrile with a CHI 650A
electrochemical analyzer.
General Procedure for the Synthesis of the Receptors
1,1 -Diacetylferrocene dihydrazone was prepared according to
Osborne et al.[29] The different receptors were prepared by
the addition of 22.0 mmol of 4-methoxy phenyl aldehyde or
∗
Correspondence to: Yan Xu, Department of Chemistry, Zhengzhou University,
Zhengzhou, 450052, People’s Republic of China. E-mail: xuyan@zzu.edu.cn
Department of Chemistry, Zhengzhou University, Zhengzhou, 450052, People’s
Republic of China
c 2009 John Wiley & Sons, Ltd.
Copyright 421
All experiments were performed under an atmosphere of dry
nitrogen with rigid exclusion of air and moisture using standard Schlenk techniques. All solvents were freshly distilled before
use according to established procedures. Other reagents were
commercially available. The melting points were obtained on a
Scheme 1. Preparation of the receptors.
C. Qiao et al.
Figure 1. The molecular structure of compound FcL1 .
dimethylene epoxy phenyl aldehyde, dissolved in ca 10 ml
methanol, was slowly added dropwise to a magnetically stirred
solution of 1,1 -diacetylferrocene dihydrazone (2.98 g, 10 mmol)
in 20 ml methanol. The mixture was refluxed for 4 h. The receptor,
which separated out with cooling at 10 ◦ C, was filtered, washed
three times with methanol and dried. The red crystals of FcL1
suitable for single-crystal X-ray diffraction analysis were gained by
slow evaporation CHCl3 at room temperature for about two weeks.
1,1 -bis[(4-methoxylphenylmethylidene)hydrazono-1ethyl]ferrocene
C30 H30 Fe N4 O2 , Yield: 86%. Anal. found: C, 67.25; H, 5.63; N,
10.33. Calcd: C, 67.42; H, 5.65; N, 10.48%. M.p.: 162–163 ◦ C, IR (KBr,
cm−1 ): 1609 s (-N CH), 1109 m (-Fc), 1025 w (-Fc). 1 H NMR (δ ppm,
CDCl3 ): 2.40 (s, J = 6.25, 6H, 2-CH3 ), 3.86 (s, J = 6.14, 6H, 2-OCH3 ),
4.44 (s, J = 4.17, 4H, 2H-3, 2H-4, ferrocenyl), 4.80 (s, J = 4.11, 4H,
2H-2, 2H-5, ferrocenyl), 6.88–7.70 (m, J = 8.1, 8H, 2-Ar), 8.36 (s,
J = 2.00, 2H, 2-CH N). UV–vis (CH3 CN) λmax : 226 nm, 313 nm.
1,1 -bis[(dimethylene epoxy phenylmethylidene)hydrazono1-ethyl]ferrocene
422
C30 H26 Fe N4 O4 , Yield: 66%. Anal. found: C, 64.28; H, 4.67; N,
9.76. Calcd: C, 64.07; H, 4.66; N, 9.96%. M.p.: 161–162 ◦ C. IR (KBr,
cm−1 ): 1602 s (-N CH), 1101 m (-Fc), 1087 w (-Fc). 1 H NMR (δ ppm,
CDCl3 ): 2.41 (S, J = 5.67, 6H, 2-CH3 ), 4.47 (s, J = 4.00, 4H, 2H-3
2H-4, ferrocenyl), 4.85 (s, J = 3.75, 4H, 2H-2 2H-5, ferrocenyl), 6.02
(s, J = 4.07, 2H, -OCH2 O-), 6.80–7.47 (m, J = 6.13, 6H, -Ar), 8.56 (s,
J = 2.12, 2H, 2-CH N). UV-Vis (CH3 CN) λmax : 229 nm, 316 nm.
X-ray single-crystal diffraction data for the FcL1 was collected
on a Bruker Smart 1000 CCD diffractometer at 291(2) K with Mo
Kα radiation (λ = 0.071073 nm). I > 2θ reflections were 4620.
The crystal structure of FcL1 is shown in Fig. 1. It belongs to the
monoclinic system P2(1)/c space group, with a = 1.9978(4) nm,
b = 0.81315 (16) nm, c = 1.7139 (3) nm, β = 106.79 (3)◦ ,
V = 2.6656 (9) nm3 , Z = 4, Dc = 1.332 mg/m3 , crystal size
0.21 × 0.20 × 0.18 mm, F(000) = 1120. The final refinement
by full-matrix least-squares was converged at R = 0.0775 and
Rw = 0.1876.
The selected bond lengths and angles of FcL1 are given
in Table 1. The mean deviations from planes C(1)–C(5) and
www.interscience.wiley.com/journal/aoc
Table 1. Selected bond lengths (Å) and angles (deg) for FcL1
C(1)–C(6)
C(20)–Fe(1)
C(21)–C(22)
C(27)–C(28)
N(1)–N(2)
N(1)–C(6)–C(7)
C(10)–C(9)–C(14)
C(8)–N(2)–N(1)
N(3)–C(21)–C(16)
O(2)–C(27)–C(28)
1.456(7)
2.039(5)
1.506(7)
1.375(7)
1.413(5)
125.2(5)
117.3(5)
124.3(4)
111.0(4)
124.9(5)
C(1)–Fe(1)
C(21)–N(3)
C(23)–N(4)
C(30)–O(2)
N(3)–N(4)
N(2)–C(8)–C(9)
C(14)–C(9)–C(8)
O(1)–C(12)–C(13)
C(23)–N(4)–N(3)
C(24)–C(29)–C(28)
2.045(5)
1.285(6)
1.267(6)
1.428(6)
1.409(6)
122.9(5)
122.9(5)
115.5(4)
113.5(5)
122.2(5)
C(16)–C(20) were all 0.0004 nm. The cyclopentodienyl rings in
ferrocenyl fragment were almost parallel with a dihedral angle of
1.65◦ . The mean deviations from rings C(9)–C(14) and C(24)–C (29)
were all 0.001 nm. The dihedral angle of two phenyl rings was 5.24◦.
The Fe–Cring distances ranged from 0.2024(6) to 0.2047(5) nm and
the intracyclopentodienyl C–C bond lengths lay in the range
0.1395(9)–0.1427 (7) nm. The C–C–C angles (average 108.0◦ )
were very similar to those reported in the literature.[30] The N–N
distances were 0.1413 and 0.1409 nm, indicating the formation of
N C double bond for both nitrogen atoms. CCDC:708123.
Electrochemical Studies
Electrochemical experiments were performed in dry acetonitrile
with CHI 650A electrochemical analyzer using a conventional three
electrode system, a GC working electrode, a Pt gauze counter
electrode and an Ag–AgCl reference electrode. All potential data
were referred to the Ag–AgCl electrode at ambient temperature
at a scan rate of 100 mV·s−1 in acetonitrile solution using TBAP
(0.1 mol·L−1 ) as the supporting electrolyte on a GC working
electrode, CV recorded from 0.20 to 1.10 (FcL1 ), 1.00 V (FcL2 ),
respectively. E 0 is defined as E 0 (receptor + cation) −E 0 (free
0
receptor). Ep = (Epa − Epc ), E = (Epa − Epc )/2. All the metal
salts used were as perclorate salts. The mole ratio of receptors and
metal salts are 1 : 1.
c 2009 John Wiley & Sons, Ltd.
Copyright Appl. Organometal. Chem. 2009, 23, 421–424
Metal ions of two new ferrocenylhydrazone-based receptors
Table 2. Electrochemical parameters of FcL1 and FcL2 (ca 5.0 × 10−4
mol·L−1 )
Compound
Epa (V)
Epc (V)
E0 (V)
Ep (V)
ipa /ipc
FcL1
FcL2
0.689
0.684
0.624
0.622
0.657
0.653
0.065
0.062
1.19
1.17
Table 3. The electrochemical kinetic data of FcL1 and FcL2
D0 × 10−5 cm2 ·s−1
Compound
CV
CC
Ks × 10−2 cm·s−1
FcL1
FcL2
1.01
0.56
0.97
0.51
3.33
5.69
Figure 2. The CVs for FcL1 and FcL1 +Mn+ in acetonitrile.
Table 4. Electrochemical response for FcL1 and FcL2 vs metal cations
in acetonitrile in 0.1 M tetrabutylammonium perchlorate (n = 3)
E0 (mV)
Receptor
FcL1
FcL2
Ag+
Ba2+
Cu2+
Zn2+
Cd2+
Hg2+
Ni2+
Cr3+
9
5
2
6
5
4
8
6
6
7
32
48
11
5
56
8
Results and Discussion
Synthesis and Characterization of the Receptors
Appl. Organometal. Chem. 2009, 23, 421–424
Figure 3. The CVs for FcL2 and FcL2 +Mn+ in acetonitrile.
receptor FcL1 to Ag+ , Ba2+ , Cu2+ , Zn2+ , Cd2+ and Ni2+ is much
lower, the same as for receptor FcL2 to Ag+ , Ba2+ , Cu2+ , Zn2+ ,
Cd2+ , Ni2+ and Cr3+ . From these electrochemical shift values, it
can be seen that the substituents on phenyl ring influence the
receptor’s characteristics greatly.
A combination of coordination properties and suitable redox
groups has proved to be a good method for strategically designing
new receptors for the electrochemical recognition of metal ions in
non-aqueous solution. It has been shown that FcL1 can be used,
through an electrochemical response, to detect Hg2+ and Cr3+ ,
and FcL2 to detect Hg2+ in a non-aqueous environment, whereas
FcL1 was unresponsive to Ag+ , Ba2+ , Cu2+ , Zn2+ , Cd2+ and Ni2+ ,
and FcL2 was unresponsive to Ag+ , Ba2+ , Cu2+ , Zn2+ , Cd2+ , Ni2+
and Cr3+ , suggesting that there is a selective sensing response.
Acknowledgments
We thank Henan Province Natural Science Foundation (no.
06110214000)
Supporting information
Supporting information may be found in the online version of this
article.
c 2009 John Wiley & Sons, Ltd.
Copyright www.interscience.wiley.com/journal/aoc
423
The receptors of FcL1 and FcL2 were prepared easily and in
good yields from 1,1 -diacetylferrocene dihydrazone with the
corresponding aldehyde in 1 : 2 molar ratio in ethanol with reflux.
The two receptors are red, stable in air and light, and are soluble
in MeOH, DMF, DMSO and CHCl3 . The elemental analysis data of
the receptors are consistent with the calculated results from the
empirical formula of each compound.
The IR spectra of the receptors were recorded in KBr and are
given with their assignments in the Experimental section.
The electrochemical parameters for FcL1 and FcL2 obtained
from the CV are summarized in Table 2. Their cyclic voltammetric
behaviors show a pair of well-defined and stable redox waves in the
potential range of 0.20–1.10 and 0.20–1.00 V at the GC electrode,
respectively, which are attributed to the Fc/Fc+ redox process. For
these two novel ferrocene hydrazone derivatives, the obtained
values of the diffusion coefficient confirm the concept that D
values decreases as the increase of the molecular weight of the
compound and as the increase of the molecular size. According to
Nicholson formula,[31] the standard rate constants of the electrode
reactions (Ks ) of two receptors are also calculated (Table 3).
The main interest in the FcL1 and FcL2 is the incorporation of
redox centers near binding sites. These redox-active groups can
be affected by the presence of metal ions and transform chemical
information at the molecular level (the presence or absence of a
target guest) into a macroscopically observable signal (shift of the
oxidation potential of the redox-active groups). The effect of metal
ions on receptor redox chemistry was investigated, and results
are shown in Table 4. The receptor FcL1 gave for Hg2+ and Cr3+
electrochemical shift up to 32 and 56 mV (Fig. 2), respectively; and
FcL2 gave for Hg2+ 48 mV (Fig. 3). However, the redox response of
C. Qiao et al.
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