Syntheses, structures of N-(substituted)-2-aza-[3]-ferrocenophanes and their application as redox sensor for Cu2+ ion

Article abstract of DOI:10.1002/aoc.2839

Rigid N-(substituted)-2-aza-[3]-ferrocenophanes L1 and L2 were easily synthesized from 1,1 -dicarboxyaldehydeferrocene and the corresponding amines. Ligands L1 and L2 were characterized by ¹H NMR, ¹³C NMR and single-crystal X-ray crystallography. The coordination abilities of L1 and L2 with metal ions such as Cu²⁺, Mg²⁺, Ni²⁺, Zn²⁺, Pb²⁺ and Cd²⁺ were evaluated by cyclic voltammetry. The electrochemical shift (ΔE_1/2) of 125 mV was observed in the presence of Cu²⁺ ion, while no significant shift of the Fc/Fc + couple was observed when Mg²⁺, Ni²⁺, Zn ²⁺, Pb²⁺, Cd²⁺ metal ions were added to the solution of L1 in the mixture of MeOH and H₂O. Moreover, the extent of the anodic shift of redox potentials was approximately equal to that induced by Cu²⁺ alone when a mixture of Cu²⁺, Mg²⁺, Ni²⁺, Zn²⁺, Pb²⁺ and Cd²⁺ was added to a solution of L1. Ligand L1 was proved to selectively sense Cu²⁺ in the presence of large, excessive first-row transition and late-transition metal cations. The coordination model was proposed from the results of controlled experiments and quantum calculations.

Full text of DOI:10.1002/aoc.2839

Full Paper
Received: 19 October 2011
Revised: 8 February 2012
Accepted: 19 February 2012
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.2839
Syntheses, structures of N-(substituted)-2-aza-
3]-ferrocenophanes and their application as
[
2
+
redox sensor for Cu ion
Lianmei Chen , Xiuling Cui *, Haitao Cheng , Xiaopei Chen ,
a
a,b
a
a
a
a
a
a
Maoping Song , Mingsheng Tang , Donghui Wei and Yangjie Wu
Rigid N-(substituted)-2-aza-[3]-ferrocenophanes L1 and L2 were easily synthesized from 1,1 -dicarboxyaldehydeferrocene and
1
13
the corresponding amines. Ligands L1 and L2 were characterized by H NMR, C NMR and single-crystal X-ray crystallography.
2
+
2+
2+
2+
2+
2+
The coordination abilities of L1 and L2 with metal ions such as Cu , Mg , Ni , Zn , Pb and Cd were evaluated by cyclic
2
+
voltammetry. The electrochemical shift (ΔE ) of 125 mV was observed in the presence of Cu ion, while no significant shift of
the Fc/Fc + couple was observed when Mg , Ni , Zn , Pb , Cd metal ions were added to the solution of L1 in the mixture of
O. Moreover, the extent of the anodic shift of redox potentials was approximately equal to that induced by Cu
alone when a mixture of Cu , Mg , Ni , Zn , Pb and Cd was added to a solution of L1. Ligand L1 was proved to selectively
1
/2
2
+
2+
2+
2+
2+
2
+
MeOH and H
2
2+ 2+ 2+ 2+ 2+ 2+
2
+
sense Cu in the presence of large, excessive first-row transition and late-transition metal cations. The coordination model was
proposed from the results of controlled experiments and quantum calculations. Copyright © 2012 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.
2+
Keywords: redox sensor; ferrocenophane; Cu
cryptands have attracted considerable attention in the last decades
because of their potential applications in the field of redox
sensors. Among these, ferrocenophane, with a rigid bridge
containing nitrogen atom, showed remarkably selective cation-
Introduction
Owing to potential applications in the analytical and environmental
areas, recent attention has been focused on the molecular sensor,
which is a rapidly growing research field of supramolecular
[
11]
sensing properties.
cules functionalized by ferrocene,
However, compared to those macromole-
[
12–15]
the number of known
[1]
science. The development of molecular sensors for metal ions,
especially for cations with biological interest, has always been of
examples of nitrogen-containing rigid macrocycles with bridged
ferrocene units is limited, partly because of the lack of general
[
2]
2+
[11,16–19]
particular interest. The Cu ion is third in abundance (after
preparation methods of the compounds and low yields.
.
2+
2+
Fe and Zn ) amongst the essential heavy metal ions in the
human body and plays a pivotal role in a variety of fundamental
physiological processes in organisms ranging from bacteria to
Here we report a feasible method to synthesize compounds L1
and L2 (Scheme 1), and investigate their coordination behaviour
with transition metal ions and alkaline earth metal ions, such as
[3]
2+
2+
2+
2+
2+
2+
2+
mammals. On the other hand, Cu can be toxic to biological
systems. Alterations in its cellular homeostasis are connected
to serious neurodegenerative diseases, including Menkes and
Cu , Mg , Ni , Zn , Pb and Cd , by cyclic voltammetry.
2+
The coordination model of Cu with L1 was proposed with the
aid of controlled experiments and quantum calculations.
[4]
[5]
Wilson diseases, familial amyotropic lateral sclerosis, Alzheimer’s
[
6]
[7]
disease and prion diseases. Thus copper, on one hand, is
important for life but, on the other hand, is highly toxic to
organisms. For these reasons, the past few years have
witnessed a number of reports on the design and synthesis of
Experimental
Silica gel was purchased from Qing Dao Hai Yang Chemical Industry
1
13
Co. H NMR and C NMR spectra were recorded on a Bruker DPX-400
[
8]
chemical sensors for the detection of copper ion. However,
the low sensitivity and high order of interference by chemical
closely related metal ions have necessitated the development
* Correspondence to: Xiuling Cui, Henan Key Laboratory of Chemical Biology and
Organic Chemistry, Key Laboratory of Applied Chemistry of Henan Universities,
Department of Chemistry, Zhengzhou University, Zhengzhou, 450052, People’s
Republic of China. E–mail: cuixl@zzu.edu.cn
2
+
of a new, highly selective and sensitive Cu sensor.
Electrochemical sensors based on optical signal measurement
represent advanced techniques in analytical chemistry because
they can be miniaturized and manufactured to monitor our
environmental samples quickly and economically, especially
heavy metal ions in situ. The cyclopentadienyl (Cp) complex
of ferrocene is easily modified and the electrochemical properties
a Henan Key Laboratory of Chemical Biology and Organic Chemistry, Key Labo-
ratory of Applied Chemistry of Henan Universities, Department of Chemistry,
Zhengzhou University, Zhengzhou, 450052, People’s Republic of China
[
9]
b Engineering Research Center of Molecular Medicine of Chinese Education Ministry,
Xiamen Key Laboratory of Ocean and Gene Drugs, Institute of Molecular Medicine
of Huaqiao University, Fujian, Xiamen 361021, People’s Republic of China
2
of the Fe(II)Cp fragment can be tuned by selecting the sub-
stituents introduced to the Cp ligand.
[
10]
Ferrocene-containing
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.

Lianmei Chen et al.
3
6
2
4
5
2
-picolylamine
Fe
N
dry DCE, NaCH(OAc)3
N
L1
CHO
CHO
Fe
2
1
1
benzylamine
3
N
Fe
dry DCE, NaCH(OAc)3
4
L2
Scheme 1. Synthesis of Ligands L1 and L2
spectrometer. Mass spectra were obtained on a Waters Q-Tof
MicroTM spectrometer. IR spectra were recorded on a Bruker VECTOR
(s, 4H, Cp&bond;H), 4.12 (s, 4H, Cp&bond;H), 2.90 (s, 4H, CH
3.87 (s, 2H, CH ph), 7.35 (dd, J = 7.3 Hz, 7.4 Hz, 2H, phenyl-H3),
7.44 (d, J = 7.4 Hz, 2H, phenyl-H2), 7.28 (t, J = 7.3 Hz, 1H,
2
Cp),
2
22 spectrometer. Element analyses were obtained on a Carlo Erba
160 element spectrometer. Melting points (uncorrected) were
13
1
3
phenyl-H4). C NMR (CDCl ): 139.5 (phenyl-C1), 129.2 (phenyl-C2),
measured on an XT5 micro-melting point apparatus.
128.7 (phenyl-C3), 126.6 (phenyl-C4), 84.2, 69.9, 68.5 (Cp-C), 61.6
(CH ph), 51.3 (CH Cp). Anal. Found: C, 72.11%; H, 6.12%; N,
All reactions were carried out under nitrogen atmosphere.
Solvents were dried and freshly distilled prior to use. All the
chemicals were used as supplied, without further purification,
except for 1,1 -dicarboxyaldehydeferrocene, which was prepared
2
2
4.50%. Calcd. for C H FeN: C, 71.94%; H, 6.04%; N, 4.42%. HRMS
1
9 19
+
(ESI). Calcd for C H FeN ([M + H] ): 318.0946. Found: 318.0942.
1
9 19
[
20]
from ferrocene according to the literature, slightly modified.
Electrochemistry
Electrochemical experiments were carried out with a CHI 650A elec-
trochemical analyzer connected to the data acquisition software
used for the electrochemical measurements. Cyclic voltammetry
experiments were performed in a glass cell enclosed in a Faraday
cage, at room temperature under argon. The reference electrode
was a 232 model saturated calomel electrode (SCE). The auxiliary
electrode was a 7.5 cm platinum wire with a gold-plated connector.
The working electrode was a glassy carbon electrode for L1 and
Synthesis of L1 and L2
1
,1 -Dicarboxyaldehydeferrocene (242 mg, 1.0 mmol) and 2-
picolylamine (109 mg, 1.01 mmol for L1; benzylamine, 108 mg,
.01 mmol for L2) in 250 ml DCE (dichloroethane) were added
simultaneously over 8 h to one four-necked 1-liter flask charged with
a solution of NaBH(OAc) (1.06 g, 5.0 mmol) in DCE (50 ml). The
1
3
mixture was stirred under N atmosphere overnight at room temper-
ature. The reaction was monitored by thin-layer chromatography
until 1,1 -dicarboxyaldehydeferrocene disappeared and quenched
2
platinum electrode for L2. The supporting electrolyte was CH OH
3
and H O containing 0.1 M KNO for L1 and CH OH containing 0.1 M
2
3
3
n
3
by saturated NaHCO solution. The solvent was concentrated under
tetrabutylammonium nitrate ( Bu NO ) for L2. Between each CV scan
4
3
vacuum to approximately 50 ml. The mixture was then extracted
the working electrode was electro-cleaned by multicycle scanning in
the supporting electrolyte solution, polished on alumina 0.3 mm,
cleaned with water–methanol and sonicated before use, accord-
ing to standard procedures. Solutions of L1 (concentration:
with CH
over Na
2
Cl
SO
2
(3 ꢀ 20 ml). The organic extracts were combined, dried
2
4
and evaporated to dryness. The oily residue was purified
by column chromatography on silica gel under reduced pressure
using hexane–acetic ether (3:1) as eluent to give the pure
compounds L1 and L2 (128.2 mg for L1, 40.3% yield and 125.1 mg
for L2, 39.5% yield) as a yellow solid.
ꢁ
3
ꢁ3
ꢁ3
1
1
.0 ꢀ 10 mol dm ; KNO : 0.1 mol dm ) and L2 (concentration:
3
ꢁ3 ꢁ3 n ꢁ3
.0 ꢀ 10 mol dm , Bu NNO : 0.1 mol dm ) were prepared.
4
3
2+
All the transition metal ions and alkaline earth metal ions (Cu ,
2+
2+
2+
2+
2+
Mg , Ni , Zn , Pb , Cd ) were from their corresponding nitrate,
ꢁ
3
L1 IR (KBr pellet): 3085, 3005, 2925, 2861, 2813, 1589, 1469, 1358,
and their concentration in 0.1 mol dm KNO
3
for L1 and 0.1 mol
for L2 were confirmed exactly by titration experi-
ment. All the CV experiments for the metal complexes were performed
ꢁ
1
1
ꢁ
3 n
1
116, 1040, 756 cm
;
H NMR (CDCl
3
) ppm: d 4.10
Cp),
2
.02 (s, 2H, CH py), 7.20 (like td, J= 7.3 Hz, 4.8 Hz,
dm
4 3
Bu NNO
(s, 4H, Cp&bond;H), 4.14 (s, 4H,Cp&bond;H), 2.96 (s, 4H, CH
2
ꢁ
1
4
1
1
immediately after solution preparation. The scan rate was 50 mV s
.
.5Hz, 1H, Py&bond;H5), 7.66 (like dd, J= 7.9 Hz,1.5Hz,
H, Py&bond;H3), 7.74 (like td, J= 7.9 Hz, 7.3 Hz, 0.9Hz, 1H,
Crystal Structure Determination
Py&bond;H4), 8.57 (like dd, J= 4.8 Hz, 0.9Hz, 1H, Py&bond;H6).
13
13
3
C NMR (CDCl ) ppm: C NMR (CDCl
3
) ppm: 160.8 (Py&bond;
All the measurements were made on a RAXIS-IV imaging plate
area detector with graphite monochromated Mo-Ka radiation
(l = 0.71073 Å). The structures were solved by direct methods
and expanded using Fourier techniques and refined by full-
matrix least-squares methods. All calculations were performed
C1), 149.1 (Py&bond;C5), 136.4 (Py&bond;C3), 123.4 (Py&bond;
C2), 121.8 (Py&bond;C4), 83.6, 69.8, 69.1 (Cp&bond;C), 63.6
(
CH Py), 52.8 (CH Cp). Anal. Found: C, 67.95%; H,5.70%; N,
2
2
8
.80%. Calcd. for C H FeN : C, 67.66%; H, 5.59%; N, 8.62%.
18 18 2
+
[21]
HRMS (ESI). Calcd for C H FeN ([M + H] ): 319.0898. Found:
using the Shelxl-97 crystallographic software package.
18
18
2
319.0951.
Yellow single crystals of L1 and L2 were developed from
the mixture of dichloromethane and hexane. L1: C H FeN ,
1
8
18
2
L2 IR(KBr): 3085, 3005, 2925, 2861, 2813, 1589, 1469, 1428,
M = 318.19, triclinic, space group. a = 6.4670(13) Å, b = 10.267(2)
Å, c = 11.232(2) Å, a = 94.64(3) , b = 98.91(3) , g = 93.80(3) ,
r
ꢁ
1
1
ꢂ ꢂ ꢂ
1358, 1116, 1040, 756 cm
;
H NMR(CDCl ) ppm: d 4.08
3
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Copyright © 2012 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2012)

2+
N-(Substituted)-2-aza-[3]-ferrocenophanes as redox sensor for Cu ion
3
ꢁ3
ꢁ1
V = 732.0(3) Å , Z = 2, D = 1.444 g cm , m(MoKa) = 1.024 mm
,
F(000) = 332. L2: C H FeN, M = 317.20, triclinic, space group.
1
9
19
r
ꢂ
a = 6.1380(12) Å, b = 11.262(2) Å, c = 11.564(2) Å, a = 94.94(3) ,
b = 101.86(3) , g = 104.38(3) , V = 749.8(3) Å , Z = 2, D = 1.405 g
cm ,m(MoKa) = 0.998 mm , F(000) = 332.
ꢂ
ꢂ
3
ꢁ
3
ꢁ1
Computational Details
The structures of ligand L1 coordinated with different metal ions
2
+
(
[ML1] (M = Mg, Ni, Pb, Cd, Zn, Cu)) were fully optimized at the
[
22]
B3LYP/Genecp level of theory.
The 6-31G (d, p) basis set was
employed for C, H, O, N atom, while the LanL2DZ basis set with
relativistic effective core potentials was used for the remaining
metal atoms. The model systems chosen for the computational
Figure 2. Crystal structure of compound L2. Selected bond lengths
Å) for L2: N(1)–C(12) 1.471(3); N(1)–C(13) 1.471(3); N(1)–C(6) 1.477(3);
(
5
5
studies were [(Z -C H )Fe(Z -C H )–(CH ) N–R] [R = pyridine and
5
4
5
4
2 2
C(11)–C(12) 1.503(3); C(13)–C(14) 1.517; C(5)–C(6) 1.504(3); selected bond
ꢂ
phenyl]. All the calculations were performed using Gaussian 03
angle( ) for L2: C(5)–Fe(1)–C(2) 69.54(10); C(11)–Fe(1)–C(2) 154.39(10);
[23]
C(1)–Fe(1)–C(2) 40.73(10); C(12)–N(1)–C(13) 109.95(18); C(12)–N(1)–C(6)
suite of programs.
112.30(18); C(13)–N(1)–C(6) 110.04(18); N(1)–C(12)–C(11) 113.30(18);
N(1)–C(13)–C(14) 113.19(19)
Results and Discussion
Synthesis of L1 and L2
The cyclopentadienyl rings in both ligands were in the eclipsed
conformation similar to the structure of the previously reported
The ligands L1 and L2 were prepared by the condensation
reaction of 1,1 -dicarbaldehydeferrocene with 2-picolylamine
and benzylamine, respectively, in DCE under highly dilute
[
24–27]
[
3]ferrocenophanes.
Two cyclopentadienyl rings (Cp) of
ꢂ
ferrocene were not parallel and formed dihedral angels of 12.9
ꢂ
and 12.1 for L1 and L2, respectively. Moreover, the two Cp rings
3
conditions and sequent reduction by NaBH(OAc) . The reac-
in both L1 and L2 were arranged in nearly eclipsed form. The
chelate cycle C5–C6–C11–C12–Fe1 in molecule L1 is nearly
planar, with the largest distance deviation 0.7598 Å of N1 and
C5, C6, C11, C12 and Fe1 atoms forming a chelate cycle with the
largest distance deviation 0.7289 Å of N1 in L2. The distances of
N1–C12, N1–C13, N1–C6 were 1.468(4), 1.471(4), 1.475(4) Å in L1
and 1.471(3), 1.471(3), 1.477(3) Å in L2, respectively. These are
normal, as the C–N distances of neutral compounds. The bond
angles are 109.2(3)–112.0(3) in L1 and the corresponding angles
of C–N1–C in L2 are 109.95(18)–112.30(18), which is slightly larger
than those of N-methylated N-hexyl-aza[3]ferrocenophanes (103
(1)–114(1)) [24b,24c].
tion was monitored by thin-layer chromatography until no 1,1 -
dicarbaldehydeferrocene was detected. The pure desired
compounds were obtained in 40.3% yield for L1 and 39.5% yield
for L2 as a light-yellow solid. L1 and L2 were characterized by
NMR, IR, MS, HRMS (ESI) and X-crystal diffraction analysis. Both
ligands were stable in the air and soluble in common solvents,
such as DCM (dichloromethane), acetone and ethyl acetate, and
less soluble in methanol and ethanol.
X-Ray Crystal Structure Analyses of L1 and L2
The molecular structures of L1 and L2 were determined by
single-crystal X-ray diffraction. Suitable single crystals for X-ray
diffraction analysis were obtained by slow evaporation from
dichloromethane/hexane at room temperature. Perspective views
of their molecular structures are shown in Figs 1 and 2, respectively.
Electrochemical Studies
Electrochemical experiments are necessary to test new redox-
responsive molecules. Therefore, cyclic voltammetry experiments
of L1 alone and in the presence of several cations were performed
in a mixture of CH
ible one-electron redox wave with a half potential (ΔE1/2) of +343
mV vs. Hg/HgCl corresponding to the ferrocene–ferrocenium
3 2
OH and H O. The ligand L1 exhibited a revers-
2
2+
couple. Addition of 0.5 equiv. of Cu resulted in two reversible
one-electron redox waves, which were assigned as redox wave
of parent ligand L1 and complex of copper with ligand in the
+
anodic region (ΔE1/2 +468 mV). The Fc/Fc couple of the parent
2+
ligand disappeared when 1.0 equiv. of Cu was added (Fig. 3).
2+
Increasing amounts of Cu up to 3.0 equiv. and prolonging the
reaction time (3 days) did not cause an obvious shift, which
2+
implied that L1 formed a stable mononuclear complex with Cu
L:M = 1:1).
Upon addition of metal ions Mg , Ni , Zn , Pb , Cd to
(
2+
2+
2+
2+
2+
Figure 1. Crystal structure of compound L1. Selected bond lengths
the solution of L1, no significant shift of the redox potential of
the Fc/Fc couple was observed (supporting information, Figs
(Å) for L1: N(1)–C(12) 1.468(4); N(1)–C(13) 1.471(4); N(1)–C(6) 1.475(4); C
+
(
11)–C(12) 1.499(5); C(13)–C(14) 1.525(5); C(5)–C(6) 1.510(5); selected
ꢂ
SI 1–5), which suggested that L1 did not have any interaction
bond angle ( ) for L1 C(12)–N(1)–C(13) 109.2(3); C(12)–N(1)–C(6) 112.0
2+
2+
with these metal ions. When a mixture of 1 equiv. Cu , Mg ,
(3); C(13)–N(1)–C(6) 109.4(3); N(1)–C(12)–C(11) 113.6(3); N(1)–C(13)–C(14)
2+
2+
2+
2+
112.6(3); N(2)–C(14)–C(15) 123.1(4); N(2)–C(14)–C(13) 114.9(4)
Ni , Zn , Pb and Cd was added to the solution of L1, the
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.
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Lianmei Chen et al.
ꢁ
1
2+
Table 1. Energy and relative excess energy (kcal mol ) of [ML1]
(
M = Mg, Ni, Pb, Cd, Zn, Cu) at B3LYP/genecp level (unit: a.u.)
Species
Energy
Excess energy Relative excess energy
Cu(NO
3
2
)
2
+
ꢁ756.7656629
[
Cu L1]
ꢁ1125.3490819 ꢁ368.583419
ꢁ626.2378383
41.84
18.76
18.58
17.06
10.73
0.00
Zn(NO )
3 2
2
+
2
[
Zn L1]
ꢁ994.7843391
ꢁ608.6898887
ꢁ977.2361029
ꢁ564.12656315
ꢁ932.6703495
ꢁ729.9404376
ꢁ368.5465008
ꢁ368.5462142
ꢁ368.54378635
Cd(NO
3
)
2
+
[
Cd L1]
Pb(NO )
3 2
+
2
[
Pb L1]
Ni(NO )
3 2
+
2
[
Ni L1]
ꢁ1098.4740958 ꢁ368.5336582
ꢁ561.5600378
Mg(NO )
3 2
+
2
[
Mg L1]
ꢁ930.0765333
ꢁ368.5164955
Figure 3. Cyclic voltammograms of L1 and its complexes with different
2
+
ꢁ1
.
amounts of Cu ions in 0.1 M KNO
3
solution. Scan rate 50 mV s
2+
Blue line, L1 only; red line, 0.5 equiv. Cu with L1; green line, 1.0 equiv
Cu ; violet line, 1.5 equiv. Cu ; orange line, 2.0 equiv. Cu ; black line,
2
+
2+
2+
2
+
3.0 equiv. Cu
extent of the anodic shift of redox potentials were approximately
2+
equal to that induced by Cu alone. These results indicated that
2+
ligand L1 selectively sense Cu ion and preferentially coordi-
2
+
nated with Cu without interference by chemically closely
related metal ions. Therefore, L1 could be a good candidate for a
molecular sensor to detect copper electrochemically in the
presence of large excesses of these first-row transition and post-
transition metal cations. The results were unexpected, because
2
+
2+
2+
the coordination behaviour of aza-ligand with Ni , Zn , Pb ,
2+
2+
Cd is normally similar to that of Cu . We suspected that the
Cu may be located in the ferrocenophane cage and only
coordinated with one nitrogen atom in the ferrocenophane chain
2+
2
+
2+
Figure 5. Relative excess energy profile of [ML1] (M = Mg, Ni, Pb, Cd,
(
Fig. 4, Model 1). Perhaps the size of the cage and radius of Cu
Zn, Cu) at B3LYP/genecp level
ion match each other very well.
To compare with L1 and test our hypothesis, ferrocenophane
L2 was synthesized by the same procedure. The electrochemical
properties were studied by cycle voltammetry. No significant
the stabilization constants have been performed at the
B3LYP/6-31G (d, p)/LanL2DZ level of theory using the Gaussian
03 program. The calculation formula of binding energy is
+
shift of the redox potential of the Fc/Fc couple was observed
2
+
when Cu ion was added. The results indicate that L1 did
2+
E ¼ E½
2þþL1ꢃ
ꢁ ðE
ꢁ 2E
ꢁÞ. The calculated results are
M
MðNO3Þ2
ðNO3Þ
not take the coordination Model 1 with Cu ion, but Model 2,
which means that Cu atom was coordinated by two nitrogen
atoms in L1.
summarized in Table 1 and Fig. 5, which show that the largest
ꢁ
1
binding energy was 41.84 kcal mol for Cu complex with L1,
2+
2+
2+
2+
2+
followed by Zn , Cd , Pb , Ni and Mg complexes. The results
2+
indicate that complex L1ꢄCu was the most stable. Moreover, the
distance between Cu and Fe is 4.123 Å (Fig. 6), longer than the sum
of their radii. The distances of Zn–Fe (2.555 Å), Cd–Fe (20769 Å),
Pd–Fe (3.117 Å), Ni–Fe (2.515 Å) and Mg–Fe (20618 Å) are shorter
than the sum of their radii, which may lead these complexes to be
unstable because of charge repulsion between the metal cations
tested and the Fe atom.
Calculation Binding Energies
Unfortunately, we failed to obtain a single crystal of Cu complex
with L1. To clarify why ligand L1 selectively sensed Cu ion in the
presence of other chemically closely related metal ions, we
applied computational studies. Quantum calculations based on
Conclusion
Fe
M
N
Fe
N
N
N
We have developed an easy methodology to synthesize ligands
M
L1 and L2. Ligand L1 was proved to be a stable and electro-
2
+
2+
Figure 4. Proposed coordination model of ligand L1 with Cu
chemically selective sensor for Cu in environments containing
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Copyright © 2012 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2012)

2+
N-(Substituted)-2-aza-[3]-ferrocenophanes as redox sensor for Cu ion
2
+
Figure 6. Representation of the optimized geometries of the [ML1] (M = Mg, Ni, Pb, Cd, Zn, Cu) at B3LYP/genecp level (units in Å for bond lengths)
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Acknowledgements
We are grateful to the NSF of China (20972139, 21102133) for
financial support of this research. The authors also thank
Prof. Dapeng Zou, Dr Weiguo Zhu and Mr Jianxun Kang from
Zhengzhou University for NMR spectra analyses and valuable
discussion.
The crystal structures of L1 and L2 have been deposited at the
Cambridge Crystallographic Data Centre and allocated the deposi-
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