The Construction of Homochiral Lanthanide Quadruple-Stranded Helicates with Multiresponsive Sensing Properties toward Fluoride Anions

Article abstract of DOI:10.1002/chem.201700827

A series of unique homochiral lanthanide tetranuclear quadruple-stranded helicates have been self-assembled controllably by using the intrinsic advantages of chiral bridging ligands, (S)-H₂L and (R)-H₂L, and lanthanide ions with high coordination numbers. The self-assembly process of these chiral helicates not only ensures the structural stability and quadruple-stranded feature of lanthanide cluster in the solid state and solution, but also achieves effective transfer and amplification of the chirality code from the ligand to a higher supramolecular level. Moreover, through using optical rotation, circular dichroism spectra analysis, and luminescence measurements, we demonstrate that these chiral lanthanide helicates could serve as sensitive and multi-responsive sensors to recognize and detect F^? anions based on the change of chiral signal and NIR luminescence simultaneously, which represents a meaningful exploration for developing functional lanthanide-based polynuclear clusters.

Full text of DOI:10.1002/chem.201700827

A Journal of
Accepted Article
Title: The Construction of Homochiral Lanthanide Quadruple-Stranded
Helicates with Multi-Responsive Sensing Properties toward
Fluoride Anions
Authors: Wanmin Chen, Xiaoliang Tang, Wei Dou, Bei Wang, Lirong
Guo, Zhenghua Ju, and Weisheng Liu
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201700827
Link to VoR: http://dx.doi.org/10.1002/chem.201700827
Supported by

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The Construction of Homochiral Lanthanide Quadruple-Stranded
Helicates with Multi-Responsive Sensing Properties toward
Fluoride Anions
[a]
Wanmin Chen, Xiaoliang Tang,* Wei Dou, Bei Wang, Lirong Guo, Zhenghua Ju, and Weisheng Liu*
Abstract: A series of unique homochiral lanthanide tetranuclear
applications in superconductive, magnetic, optical, electronic,
[10]
quadruple-stranded helicates have been self-assembled controllably
and catalytic processes.
The main reasons may be due to
by taking the intrinsic advantages of chiral bridging ligands, (S)-H
2
L
uncontrollability of polynuclear arrangement and inherent nature
of lanthanide ions, including their high coordination numbers,
kinetic lability, weak stereochemical preference and more
variable nature of the coordination sphere, which might exhibit
uncertain stereochemistry so that the molecular structures and
frameworks of lanthanide complexes could not be well regulated
and (R)-H L, and lanthanide ions with high coordination numbers.
2
The self-assembly process of these chiral helicates not only ensures
the structural stability and quadruple-stranded feature of lanthanide
cluster in solid and solution, but also achieves the effective transfer
and amplification of chirality code from ligand to higher
supramolecular level. Moreover, through using optical rotation,
circular dichroism spectra analysis and luminescence measurement,
we demonstrate that these chiral lanthanide helicates could serve as
[
9,10]
or predicted.
Lehn, Bünzli, Piguet, Gunnlaugsson and a few
pioneers have investigated a series of lanthanide helicates
constructed by multidentate ligands in detail and focused on the
‒
[10,11]
sensitive and multi-responsive sensors to recognize and detect F
preparation of helicates,
but the controllable self-assembly
anions based on the change of chiral signal and NIR luminescence
and application of chiral lanthanide-based polynuclear helicates
accompanied with chiral signal change also remain a great
challenge and need to be explored further.
simultaneously, which represents
a meaningful exploration for
developing functional lanthanide-based polynuclear clusters.
On the other hand, the signal transduction for selectively
recognizing or detecting anions is a significant topic in analysis
[
12]
technology as well as environmental science.
As one of the
Introduction
essential microelements in the human body, a certain amount of
‒
F as additive in toothpastes and water can prevent dental caries
Chirality is one of the intrinsic features of nature and plays such
a vital role in natural and life sciences that it is called signature
‒
effectively, but excessive ingestion of F may cause fluorosis,
leading to a series of skeletal diseases, mottled teeth, kidney
[
1]
of life. Many efforts have been devoted to the structural design
and utilization of enantiopure compounds or supramolecular
[13]
‒
disorders and urolithiasis. Therefore, the monitoring of F with
[14]
high electronegativity has received considerable attention. At
present, most of F -selective signal recognition studies are
[
2]
assemblies due to the strong demand for chiral properties in
the fields of asymmetric catalysis, enantioselective separation,
‒
based on ion chromatography and fluorescent chemosensor, but
[3]
nonlinear optical materials, bioscience and pharmaceuticals.
[15]
other detection methods are rarely employed and exploited.
Among various strategies to synthesize chiral substances,
transition metal center-directed self-assembly incorporated with
chiral functional groups in ligand not only provides directly
excellent opportunities to widen the research scope of chiral
materials, but also establishes a platform for chirality induction,
‒
Thus, the utilization of chirality signal to trace F may be a
promising and new strategy, which provides
supplement for F -selective recognition in analytical method.
We have been interested in the construction of novel chiral
a beneficial
‒
lanthanide helicates through using enantiomorphous ligands to
[
4]
inversion and transfer. There is a great deal of progress in the
construction of chiral transition metal complexes, such as
[9b,9e]
develop new recognition function.
To controllably prepare
lanthanide-based polynuclear helicates and extend application
of chiral complex in information transfer, a pair of homochiral
[5]
[6]
[7]
helicates, cage complexes, coordination polymers, and
[
8]
metal-organic frameworks (MOFs). However, the research of
chiral lanthanide complexes, especially chiral polynuclear
clusters, is less well understood, although lanthanide ions
possess special electronic configuration and their complexes are
ideal candidates for fascinating structures and potential
2 2
bridging ligands, (S)-H L and (R)-H L ( (1S, 2S)- and (1R, 2R)-
1
2
N' ,N' -bis(3-ethoxy-2-hydroxybenzylidene)cyclohexane-1,2-
dicarbohydrazide), were designed by the introduction of
enantiomerically pure and disubstituted cyclohexyl group. Two
enantiomorphous ligands with rigid and folded framework
possess acylhydrazone groups linked together with phenol
moiety at the two termini, which not only provides tridentate
coordination site to capture lanthanide ion, but also can transfer
directly energy to sensitize the luminescence of metal ion as
antenna group. Moreover, the existence of two hydroxyl oxygen
atoms and two ether oxygen atoms could bridge other
lanthanide ions to form polynuclear arrangement.
[
9]
[
a]
W. Chen, Dr. X. Tang, Dr. W. Dou, B. Wang, L. Guo, Z. Ju, Prof. Dr.
W. Liu
Key Laboratory of Nonferrous Metal Chemistry and Resources
Utilization of Gansu Province and State Key Laboratory of Applied
Organic Chemistry, Key Laboratory of Special Function Materials
and Structure Design, Ministry of Education, College of Chemistry
and Chemical Engineering, Lanzhou University, Lanzhou, 730000,
China
Herein, we report two pair of unique and enantiomerically pure
Fax: (+86) -931-8912582
chiral
lanthanide-based
tetranuclear
quadruple-stranded
E-mail: tangxiaol@lzu.edu.cn, liuws@lzu.edu.cn
helicates, which are self-assembled by different lanthanide ions
‒
and homochiral ligands with the aid of NO
3
anion template
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
under mild conditions. And more importantly, the homochiral
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Figure 1. a) Synthesis of a homochiral bridging ligand by the introduction of disubstituted and enantiomerically pure cyclohexyl group, and structural formula of
3+
3
+
the chiral ligand with potential multi coordiantion sites capturing lanthanide ions. b) Capped sticks representation of [La
4
{(R)-L}
4 3
(NO )] (1a) containing four La
2‒
–
ions and four (R)-L ligands. The triangular NO ion is encapsulated by ligands and shown in a space-filling representation. Each of ligand is represented in a
different color, and element La is violet. c) The coordination pattern of each ligand (R)-L in helicate from different perspectives. All four La ions are bridged by
3
2‒
3+
–
3
NO
ion to form a twisted rectangle. d) Space-filling representation of the homochiral lanthanide tetranuclear quadruple-stranded M helical structure.
‒
lanthanide helicate further displayed high selectivity toward F in
chiral signal as well as turn-on luminescent response in near-
infrared region, which represents the successful exploitation of
the chiral lanthanide supramolecular structure and function.
X-ray crystallographic analysis revealed that four quadruple-
stranded helicates 1a, 1b, 2a and 2b crystallized in chiral space
groups (Table S1). In all compounds, the helical cluster cations,
3
+
2–
2–
4 4 3
[Ln L (NO )] (L = the deprotonated ligand (R)-L or (S)-L ),
are similar and each of them is composed of four deprotonated
chiral ligands, four lanthanide ions, and an encapsulated nitrate
in the center. Therefore, the crystal structure of 1a is depicted
here in detail for the sake of brevity.
Results and Discussion
3
+
4 4 3
In the cluster [La {(R)-L} (NO )] , disubstituted cyclohexyl
group with boat form in the middle of ligand restrains the variety
of ligand chain, and whole ligand presents rigid and V-shaped
framework. The acylhydrazone group accompanied with phenol
Synthesis of chiral lanthanide helicates
The chiral bridging ligands, (R)-H
prepared by the reaction of chiral (1R, 2R) and (1S, 2S)-
cyclohexane-1,2-dicarbohydrazide with 3-ethoxy-2-
2 2
L and (S)-H L, were first
3
+
moiety provides tridentate coordination fashion, and two La
ions are captured effectively into tridentate coordination sites,
respectively, on both ends of rigid ligand (Figure 1b). Each of
hydroxybenzaldehyde, respectively (Figure 1a and Scheme S1).
Then, single chiral quadruple-stranded helicates were
3
+
La ions is chelated by two acylhydrazone moieties from
different ligands, and is further chelated by the deprotonated
phenolic oxygen atom and ether oxygen atom from the third
ligand in a bidentate mode. In addition, the nitrate group in the
center of cluster offers oxygen atoms participates in the
synthesized by the addition of a solution of Ln(NO
La, Nd) in methanol to a pale yellow and transparent solution of
R)-H L or (S)-H L and LiOH·H O (1:2 molar ratio) in a mixed
solution of methanol and acetonitrile. Yellow diamond crystals of
Ln {(R)-L} (NO )]·3NO ·xCH OH·yH O·zCH CN (Ln = La (1a),
Nd (2a)) or [Ln {(S)-L} (NO )]·3NO ·xCH OH·yH O·zCH CN (Ln
La (1b), Nd (2b)) suitable for X-ray diffraction were obtained in
3 3 2
) ·6H O (Ln =
(
2
2
2
3
+
coordination of La ions, and finally the coordination polyhedra
[
4
4
3
3
3
2
3
3
+
around each of La ions can be best described as slightly
4
4
3
3
3
2
3
3
+
distorted tricapped trigonal prisms (Figure S1). Four La ions
form a slightly twisted rectangle and they could be divided into
=
good yield by slow evaporation of the solution in air at room
temperature within a week.
3
+
two groups, in each of which two closer La ions are bridged by
two deprotonated phenolic oxygen atoms to form double metal
cluster unit, and the distances of La ··· La are 3.99 Å and 4.08 Å,
respectively (Figure 1c). Two pairs of double metal clusters are
linked and wrapped by four ligands, and the distances of
La ··· La as longer side of twisted rectangle are 5.99 Å and 6.12
Structural features of chiral helicates
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Å, respectively. Thus, all chiral bridging ligands twine orderly
around four lanthanide ions along the fixed spiral direction,
resulting in the formation of homochiral tetranuclear quadruple-
stranded M helicate structure (Figure 1d). That is, the chirality
code of ligand is effectively transferred and amplified towards
the higher supramolecular level with the participation of
lanthanide ions.
Another notable structural feature of these helicates is that all
3
+
four La ions are coordinated and linked closely by the central
–
1 1 2
NO
3 4
anion, which adopts a μ -η η η bridging mode as second
ligand. As shown in Figure 1c, one of oxygen atoms in nitrate
bridges two lanthanide ions and the other two oxygen atoms
coordinate with the rest two lanthanide ions, respectively. The
La ··· O distances are within the normal range of 2.59 Å to 2.66
–
Å. The bridging NO
cluster [La {(R)-L}
3
anion occupies the nucleation site of
)] , and serves as an important template
3
+
4
4
(NO
3
part in self-assembly of the chiral quadruple-stranded helicate.
In other words, the homochiral cluster structure is further
–
stabilized by the introduction of the NO
3
anion.
Characterization of chiral lanthanide helicates
The self-assembly of chiral helicates and the template effect of
Figure 2. a) HRESI mass spectra of 1a in methanol and the assignments of
spectral peaks. b) Magnification of the mass peaks at m/z = 864.8266 with
isotopic distribution patterns separated by (0.33 ± 0.005) Da. Inset: Theoretical
–
the NO
3
anion in the cluster core were further investigated by
using IR, NMR and mass spectrographic analysis. FT-IR spectra
of all helicates in solid state showed clearly that the
characteristic strong bands for stretch vibrations ν(C=O) at 1660
3+
4 4 3
HRESI mass spectra of [La {(R)-L} (NO )] at m/z = 864.8264 and isotopic
distribution patterns.
‒
1
‒1
cm and ν(Ar‒OH) at 1250 cm of free ligands shift towards
‒
1
‒1
lower wave numbers by ~30 cm and ~32 cm , respectively,
indicating that amide groups and phenol groups in ligand take
part in coordination to lanthanide ions and result in the formation
of new structure. In addition, strong nitrate-based vibrations at
384 cm , which are not observed for ligands, are presented in
the spectra of helicates, suggesting that NO
directly evidence for the formation of stable chiral lanthanide
quadruple-stranded helicates encapsulated with nitrate anion in
the solution. Moreover, the mass peaks at m/z = 1328.2335 and
1296.7361 with isotopic distribution patterns separated by (0.50
± 0.005) Da can be attributed to the derivative ions of helicates
‒
1
1
–
3
anions are fixed
2
+
{
[La
4
{(R)-L}
4
(NO
3
)]·NO
3
}
(calculated m/z = 1328.2336) and
(calculated m/z 1296.7358),
respectively (Figure S4 and Figure S5).
firmly in complexes (Figure S2).
2
+
–
[La {(R)-L} (NO )–H]
=
4
4
3
In order to discuss the role NO
replace La(NO
early stage during preparation process of complex, and then,
NaNO in methanol was added. The obtained crystals were
3
plays, LaCl
3
was employed to
3 3 2
) and react with deprotonated (R)-H L at the
3
Chiral analysis of lanthanide helicates
consistent with chiral tetranuclear quadruple-stranded cluster 1a,
which was confirmed by X-ray crystallographic analysis.
Meanwhile, 15N isotopic labeled NaNO
state N NMR spectrum showed clearly that a weak peak with
3
was used and solid-
To study the effects of chiral ligand on self-assembly of
lanthanide helicates and understand the remarkable chirality
transfer process from the ligand to cluster, the homochiral 1b
1
5
low intensity appeared at δ = 384.12 ppm, which can be
–
ascribed to the encapsulated NO
3
in the center of helicate
was prepared by employing (S)-H
2 2
L in place of (R)-H L. As
–
3+
(
Figure S3). Thus, strong binding ability of NO
3
in tetranuclear
expected, the crystal of enantiomer [La {(S)-L} (NO )] was
4 4 3
quadruple-stranded cluster structure was revealed and the
successfully obtained, and four ligands form a tetranuclear
quadruple-stranded helix as well as 1a, but with the opposite P
helical configuration (Figure 3a, Figure S6). However, when
–
3
important templating function of NO anion was well presented.
To confirm the stability of these chiral tetranuclear quadruple-
stranded helicates in the solution, high-resolution electrospray
ionization mass spectra (HRESI-MS) of 1a was performed. As
shown in Figure 2, the presence of the intense peaks at m/z =
2 2
racemic compound H L, with equal amounts of chiral (R)-H L
and (S)-H L, was selected as ligand, we also could get
2
tetranuclear quadruple-stranded lanthanide clusters under the
same conditions, but they crystallized in achiral and
8
0
L}
64.8266 with isotopic distribution patterns separated by (0.33 ±
.005) Da easily belongs to positively charged [La {(R)-
)] cluster (calculated m/z = 864.8264), which is in good
̅
centrosymmetric space group 푃1. In complex 1, two kinds of
4
3+
(NO
3
lanthanide helicates with M helical configuration and P helical
4
agreement with the theoretical isotopic distribution and provides
configuration arranged and self-assembled alternatively in three
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Figure 3. a) Molecular configurations and the relationship with the mirror
image of two chiral bridging ligands (R)-H
could self-assemble respectively with lanthanide ions to form corresponding M
and P helical tetranuclear quadruple-stranded clusters. Two helicates with
2
L (left) and (S)-H
2
L (right), which
Figure 4. a) Optical rotation responses of 1a to different anions in methanol.
–3
λ= 589 nm, [1a] = 4 × [anion] = 4 × 10
M. b) The CD change of 1a upon
‒
addition F in methanol. Inset: The CD intensity at 400 nm as a function of
‒
– 4
mirror image are shown in
a
space-filling representation, and the chiral
[F ]/[1a]. [1a] = 5 × 10 M.
information of ligands is transfered and amplified. Hydrogen atoms, solvent
molecules and uncoordinated anions are omitted for clarity. Each ligand is
represented in a different color and the lanthanide ions are shown in violet. b)
Solid-state CD spectra of 1a and 1b in KCl pellets, which present mirror image.
bond donors in acylhydrazone groups and uncoordinated
counter anions (Table S2), the responses of homochiral
lanthanide helicates on different anions in optical rotation and
circular dichroism (CD) spectra were subsequently investigated
in solution. We measured the optical rotation of 1a in methanol
dimensions to form racemic supramolecule (Figure S7). As
confirmed by solid-state circular dichroism (CD) spectroscopy,
crystals of both 1a and 1b in KCl pellets exhibited stronger
circular dichroism signals with positive and negative Cotton
effect, respectively, which present mirror-image CD spectra with
opposite signs (Figure 3b). But there is no any signal for 1 in CD
spectra due to the ordered packing of two kinds of different
helicates. Therefore, the chirality and purity of ligands could be
preserved and transferred effectively towards complex helical
system.
‒
‒
‒
‒
‒
‒
‒
‒
solution in the presence of F , Cl , Br , I , NO
3
, BF
4 4 3
, ClO , N ,
‒
‒
-
‒
SCN , CF
3
SO
3
, OH and HSO
4
, respectively. The results
showed that a significant enhancement in optical rotation could
‒
be observed only for F , but no clear change for other anions in
‒
the same conditions, which suggested that F anion with strong
electronegativity might take part in the exchange of counter
anions and the formation of hydrogen bonds so that the optical
rotation value of chiral 1a was changed and magnified (Figure
4
a). CD spectra of 1a in methanol solution at the range of 200‒
‒
500 nm also exhibited the selective response only for F . As
shown as Figure 4b, the CD intensity of 1a at 254, 308 and 400
Recognition of chiral lanthanide helicates
nm decreased gradually but the CD intensity at 235 and 280 nm
‒
increased with the increase of F , which stopped changing
The prominent structural stability and optical pure chiral features
of these lanthanide tetranuclear quadruple-stranded helicates
intrigued us to further explore their sensing applications based
on chiral signal. Considering that there are a lot of hydrogen
‒
further when two equiv F were added and accompanied by the
formation of three isosbestic points at 247, 262 and 297 nm.
‒
These results clearly suggested that the introduction of F could
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‒
Figure 5. The NIR emission spectra change of 2a upon addition F (0-2 equiv)
in acetonitrile. Inset: The emission intensity of 2a at 1060 nm as a function of
‒
– 4
[
F ]/[2a]. [2a] = 1.0 × 10 M, λex = 380 nm.
Figure 6. The recognition mechanism of chiral lanthanide-based tetranuclear
‒
–
helicates for F anion. The uncoordinated NO
3
anions around the helicate
‒
could be replaced with F anions to form strong N‒H···F hydrogen bonds and
induce aggregation or supramolecular self-assembly of many chiral helicates.
Hydrogen bonds are denoted by blue broken line.
influence the aggregation of chiral helicates and cause the
change of chiral signal of helicates. Thus, optical rotation and
CD analysis of the chiral lanthanide helicates, as simply and
‒
sensitively new tools, could be applied to F anion selective-
recognition, which has not been reported to date.
optical rotation and CD spectra, but also could stabilizes the
structure of lanthanide helicates to weaken non-radiative
On the other hand, as an important near-infrared (NIR)
3+
transitions of Nd
ion, showing turn-on NIR luminescent
3
+
materials, Nd ion with its sharp emission band centered at
060 nm could be identified specifically and has potential
applications in night vision, energy conversion, tracking, sensing,
response. Therefore, the lanthanide helicates displayed
1
‒
recognition of multi-model responses toward F anion both in
chiral signal and NIR luminescence, which provides
a
[
16]
optical communication, anti-counterfeiting printing, and so on.
Two enantiomeric homochiral tetranuclear quadruple-stranded
meaningful exploitation of the lanthanide supramolecular
structure and function.
3
+
helicates 2a and 2b were also self-assembled by Nd ions and
corresponding chiral ligands, respectively (Figure S8 and S9),
and the chirality of ligand played a vital role for structural feature
of homochiral helicate (Figure S10). 2a exhibited strong
Conclusions
3
+
characteristic emission of the Nd ion at 1025-1125 nm, which
4
4
In conclusion, we have designed a pair of chiral bridging ligands
by the introduction of enantiomerically pure cyclohexyl group,
which could effectively coordinate and self-assemble with
lanthanide ions to form enantiomerically pure chiral lanthanide-
can be assigned to the
3/2
F → I9/2 transition, pointing toward
3
+
efficient sensitization of Nd ion. The sensing property of 2a
towards F was monitored in methanol, and it exhibited chiral
‒
responses similar to 1a in optical rotation and CD spectra
based tetranuclear quadruple-stranded helicates with the aid of
(
Figure S11 and S12). More importantly, the luminescent
‒
NO
3
anion template under mild conditions. The self-assembly
spectra of 2a showed that the characteristic luminescent
3
+
process of these unique chiral helicates not only ensured the
structural stability and quadruple-stranded feature of lanthanide
cluster in solid and solution, but also achieved the effective
transfer and amplification of chirality code from ligand to higher
supramolecular level. Meanwhile, through using optical rotation,
CD spectra analysis and luminescence measurement, we found
that the chiral lanthanide helicates could serve as sensitive and
intensity of Nd at 1060 nm increased rapidly with the amount of
‒
‒
F
until two equiv F were added (Figure 5), a turn-on near-
‒
infrared luminescent response toward F was observed clearly
that is rarely reported now.
On the basis of the above results, a sensing model of the
‒
homochiral tetranuclear lanthanide helicates toward F anion
might be proposed that involves the formation of hydrogen
‒
multi-responsive sensors to recognize and detect F based on
bonds and supramolecular self-assembly of helicates. In solution,
‒
the change of chiral signal and NIR luminescence
simultaneously, which represents an innovative and meaningful
exploration for the chiral lanthanide supramolecular structure
and function. Thus, the understanding of self-assembly
mechanism based on chiral transfer might be able to bring more
opportunity to develop functional lanthanide-based polynuclear
clusters.
F
anions possess strong electronegativity and they could
–
exchange with uncoordinated NO
3
anions to approach
acylhydrazone groups in ligand and form many strong N‒H···F
hydrogen bonds, which may lead to the aggregation or self-
assembly of chiral helicates to some extent (Figure 6). The
‒
supramolecular interactions between helicates and F anions not
only results in the change of chiral signals of helicates both in
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Chemistry - A European Journal
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Synthesis of complexes
Experimental Section
[
La
LiOH·H
methanol (3 mL) was stirred for 5 min, then a solution of La(NO
4
{(R)-L}
4
(NO
3
)]·3NO
3
·xCH
3
OH·yH
2
O·zCH
L (24.8 mg, 0.05 mmol) in
2
·6H O
3
CN (1a): A mixture of
Materials and instrumentation: All the materials for synthesis were
purchased from commercial suppliers and used without further
purification. All of the solvents used were of analytical reagent grade and
deionized water was used. H NMR and C NMR spectra were recorded
on a JNM-ECS-400 MHz spectrometer and the chemical shift in ppm and
using tetramethylsilane as internal reference. Mass spectra (ESI) for
organic compounds were performed on a Bruker Daltonics Esquire 6000
mass spectrometer. HRESI-MS for complexes were performed on
Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. FT-IR
spectra were recorded in KBr pellets on a NEXUS 670 in the region
2
O (4.2 mg, 0.1 mmol) and (R)-H
2
3
)
3
1
13
(21.7 mg, 0.05 mmol) in methanol and acetonitrile (2 mL, v/v, 2:1) was
added and the mixture was rapidly stirred for 5 min. The yellow crystals
suitable for X-ray analysis were obtained 65 % yield by slow evaporation
of the solution within one week at room temperature in air. Elemental
analysis (%) calcd. for complex 1a C104
solvent molecules were lost upon drying): C 44.90, H 4.35, N 10.07;
found: C 44.79, H 4.25, N 10.15. HRESI-MS m/z: 864.8266 [La {(R)-
L} (NO )] (calcd. for C104H La N17O , 864.8264), 1296.7361 [La {(R)-
4 20
H120La N O36 (non-coordinated
4
3+
-
1
4
000−400 cm . Elemental analyses (C, H, N) were performed on a Vario
4
3
120
4
27
4
2+
15
L} (NO )–H] (calcd. for C104H119La N17O27, 1296.7358), 1328.2335
{
EL elemental analyzer. Solid-state N high-power decoupling (HPDEC)
NMR spectra were performed with a 4-mm double-resonance MAS probe
on Bruker Avance II WB 400 MHz spectrometer. The solution CD spectra
were recorded on an Olis DSM 1000 spectropolarimeter. Solid-state CD
4
3
4
2+
[La
4
{(R)-L}
4 3 3
(NO )]·NO }
4 18
(calcd. for C104H120La N O30, 1328.2336). IR
-
1
(KBr, cm ): 3436 (br), 3226 (m), 3052 (w), 2975 (w), 2931 (m), 2860 (w),
1
1
8
631 (m), 1605 (vs), 1556 (s), 1450 (s), 1384 (vs), 1304 (s), 1262 (w),
219 (vs), 1174 (m), 1112 (w), 1096 (w), 1070 (m), 1044 (w), 938 (w),
91 (m), 855 (w), 740 (s), 641 (w).
spectra measurements were performed on
a
JASCO J-810W
spectrophotometer at room temperature. The steady-state luminescence
spectra were performed on Edinburgh Instrument FSL920 fluorescence
spectrometer. Optical rotations were measured at 20 °C in methanol on a
Perkin-Elmer Model 341 polarimeter.
[La
1b was synthesized by the same procedure as that for 1a, except that
S)-H L was used instead of (R)-H L. The crystals of 1b were obtained in
2 % yield by slow evaporation of the mixed solution within one week at
room temperature in air. Elemental analysis (%) calcd. for complex 1b
36 (non-coordinated solvent molecules were lost upon
drying): C 44.90, H 4.35, N 10.07; found: C 44.74, H 4.30, N 9.95. IR
4 4 3 3 3 2 3
{(S)-L} (NO )]·3NO ·xCH OH·yH O·zCH CN (1b): The enantiomer
(
6
2
2
Synthesis of homochiral ligands
C
104 4 20
H120La N O
Synthesis
of
ligand
2
(R)-H L:
(1R,2R)-Cyclohexane-1,2-
dicarbohydrazide was prepared first according to Scheme S1. To a
solution of (1R,2R)-cyclohexane-1,2-dicarbohydrazide (0.80 g, 4.0 mmol)
in ethanol (25 mL) was added 3-ethoxy-2-hydroxybenzaldehyde (1.36 g,
-
1
(KBr, cm ): 3436 (br), 3240 (m), 3053 (w), 2975 (w), 2931 (m), 2860 (w),
1
1
8
632 (m), 1605 (vs), 1555 (s), 1450 (s), 1384 (vs), 1307 (s), 1261 (w),
219 (vs), 1174 (m), 1113 (w), 1095 (w), 1070 (m), 1044 (w), 938 (w),
91 (m), 855 (w), 741 (s), 642 (w).
8
.2 mmol) in ethanol (10 mL). This mixture was then stirred and allowed
to stand for 6 h at 40 °C. The white precipitate was filtered off and
washed with diethyl ether, and dried in vacuo to obtain ligand (R)-H L as
2
white solid (1.60 g, yield 80.5 %). m.p. 247.6–248.5 °C. [훼] 0= –29.0 cm
2
3
[La L (NO )]·3NO ·xCH OH·yH O·zCH CN (1): The racemic
1
was
synthesized by the same procedure as that for 1a, except that the
racemic mixture of (R)-H L and (S)-H L was used instead of chiral (R)-
4
4
3
3
3
2
3
퐷
–
1
–1
g
dm (The ligand exhibited poor solubility, which could be dissolved
–3
by addition of NaOH to become (R)-Na
methanol). H NMR (400 MHz, DMSO-d ): δ = 11.72 (d, J = 16.4 Hz,
2
L, c = 0.01 g cm (R)-Na
2
L in
2
2
1
H L. The crystals of 1 were obtained in 58 % yield by slow evaporation of
the mixed solution within one week at room temperature in air. Elemental
analysis (%) calcd. for complex 1 C104
solvent molecules were lost upon drying): C 44.90, H 4.35, N 10.07;
2
6
1
0
2
.40H), 11.14 (s, 0.6H), 10.83 (d, J = 21.6 Hz, 1.4H), 9.54 (d, J = 21.2 Hz,
4 20
H120La N O36 (non-coordinated
.6H), 8.32 (d, J = 22.0 Hz, 2H), 6.78–7.20 (m, 6H), 4.02–4.08 (m, 4H),
13
.50–2.63 (m, 1.4H), 1.79–2.05 (m, 4H), 1.30–1.38 (m, 10H). C NMR
): δ = 175.57, 171.01, 170.69, 147.44, 147.20,
-
1
found: C 44.80, H 4.23, N 10.16. IR (KBr, cm ): 3436 (br), 3240 (m),
(100 MHz, DMSO-d
6
3053 (w), 2975 (w), 2931 (m), 2860 (w), 1632 (m), 1605 (vs), 1555 (s),
1450 (s), 1384 (vs), 1307 (s), 1261 (w), 1219 (vs), 1174 (m), 1113 (w),
1095 (w), 1070 (m), 1044 (w), 938 (w), 891 (m), 855 (w), 741 (s), 642 (w).
1
1
1
47.10, 146.73, 146.50, 146.32, 141.65, 121.11, 120.39, 119.48, 119.08,
15.20, 114.17, 64.22, 44.11, 43.88, 41.58, 29.72, 28.49, 25.47, 25.20,
4.90, 14.83. ESI-MS m/z: calcd. for
C H N O
26 32 4 6
+
496.2322 and
-1
C
26 32 4 6
H N O Na 519.2220, found: 519.2217 [M+Na] . IR (KBr, cm ): 3435
(br), 3203 (m), 3060 (m), 2979 (m), 2929 (s), 2859 (m), 1655 (vs), 1609
(m), 1576 (w), 1547 (s), 1464 (vs), 1389 (s), 1353 (w), 1264 (w), 1248
(vs), 1190 (m), 1115 (m), 1077 (m), 1050 (w), 957 (w), 936 (w), 897 (w),
[Nd
synthesized by the same procedure as that for 1a, except that
Nd(NO ·6H O was used instead of La(NO ·6H O. The crystals of 2a
4 4 3 3 3 2 3
{(R)-L} (NO )]·3NO ·xCH OH·yH O·zCH CN (2a): Complex 2a was
3
)
3
2
3
)
3
2
833 (w), 780 (w), 733 (s), 639 (w).
were obtained in 58 % yield by slow evaporation of the mixed solution
within one week at room temperature in air. Elemental analysis (%) calcd.
for complex 2a C104
4 20
H120Nd N O36 (non-coordinated solvent molecules
Synthesis of ligand (S)-H
the same procedure as that for (R)-H
cyclohexane-1,2-dicarboxylic acid was used instead of the starting
2
L: The enantiomer (S)-H
2
L was prepared by
were lost upon drying): C 44.56, H 4.31, N 9.99; found: C 44.78, H 4.20,
2
L, except that (1S,2S)-
-
1
N 9.98. IR (KBr, cm ): 3437 (br), 3205 (m), 3051 (w), 2975 (w), 2930 (m),
2
1
8
859 (w), 1631 (m), 1605 (vs), 1557 (s), 1448 (s), 1384 (vs), 1301 (s),
263 (w), 1221 (vs), 1174 (m), 1097 (w), 1070 (m), 1043 (w), 938 (w),
92 (m), 856 (w), 741 (s), 642 (w).
material (1R,2R)-cyclohexane-1,2-dicarboxylic acid. The enantiomer (S)-
H
2
L was obtained as white solid in 42.0 % total yield (3-Step reactions
with (1S,2S)-cyclohexane-1,2-dicarboxylic acid as the starting material).
20
3
–1
–1
[
훼] = +29.0 cm
g
dm (The ligand exhibited poor solubility, which
could be dissolved by addition of NaOH to become (S)-Na L, c = 0.01 g
L in methanol). IR (KBr, cm ): 3434 (br), 3210 (m), 3060 (m),
979 (m), 2929 (s), 2859 (m), 1656 (vs), 1609 (m), 1577 (w), 1546 (s),
퐷
2
[Nd
2b was synthesized by the same procedure as that for 2a, except that
(S)-H L was used instead of (R)-H L. The crystals of 2b were obtained in
53 % yield by slow evaporation of the mixed solution within one week at
room temperature in air. Elemental analysis (%) calcd. for complex 2b
4 4 3 3 3 2 3
{(S)-L} (NO )]·3NO ·xCH OH·yH O·zCH CN (2b): The enantiomer
–3
-1
cm (S)-Na
2
2
1
1
6
2
2
464 (vs), 1388 (s), 1353 (w), 1264 (w), 1248 (vs), 1190 (m), 1115 (m),
077 (m), 1051 (w), 960 (w), 936 (w), 897 (w), 833 (w), 780 (w), 732 (s),
37 (w).
C
104
H
120Nd
4
20
N O36 (non-coordinated solvent molecules were lost upon
drying): C 44.56, H 4.31, N 9.99; found: C 44.85, H 4.52, N 10.15. IR
-
1
(
KBr, cm ): 3437 (br), 3212 (m), 3052 (w), 2975 (w), 2930 (m), 2859 (w),
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1
1
631 (m), 1605 (vs), 1557 (s), 1448 (s), 1384 (vs), 1302 (s), 1263 (w),
220 (vs), 1174 (m), 1097 (w), 1070 (m), 1043 (w), 938 (w), 891 (m), 855
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(
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Single crystal X-ray crystallography: Single-crystal X-ray diffraction
measurements were carried out on a Bruker SMART APEX-II CCD
diffractometer (1a, 1b, 1) and an Agilent SuperNova system (2a, 2b)
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Entry for the Table of Contents
FULL PAPER
Homochiral Lanthanide Helicates:
Homochiral Lanthanide tetranuclear
quadruple-stranded helicates were
synthesized by chiral bridging ligands,
which exhibit stable structure and
achieve the effective transfer and
amplification of chirality code.
Meanwhile, the chiral lanthanide
helicate could apply to F‒ anions
detection with multi-model responses
both in chiral signal and NIR
Wanmin Chen, Xiaoliang Tang,* Wei
Dou, Bei Wang, Lirong Guo, Zhenghua
Ju, and Weisheng Liu*
Page No. – Page No.
The Construction of Homochiral
Lanthanide Quadruple-Stranded
Helicates with Multi-Responsive
Sensing Properties toward Fluoride
Anions
luminescence.
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