High-Nuclearity Cd(II)-Nd(III) Nanowheel with NIR Emission Sensing of Metal Cations and Nitro-Based Explosives

Article abstract of DOI:10.1021/acs.cgd.0c01742

One Cd-Nd nanowheel [Cd8Nd4L8(OAc)8]·4OH (1, molecular sizes: 1.2 × 2.8 × 2.8 nm) was obtained by using one designed flexible Schiff base ligand containing eight coordination sites. The Schiff base ligand exhibits a hexadentate η1:η2:η1:η1:η2:η1:μ4 coordination mode. The chromogenic Cd/L components are able to transfer energy to Nd(III), leading to the near-infrared (NIR) lanthanide emission of 1. The energy transfer efficiency (ηsens) is calculated to be 39.4%. 1 shows interesting luminescent sensing activity toward metal cations and nitro-based explosives, in particular to Cu(II), Fe(III), Co(II), and 2,4,6-trinitrophenol (TNP) with high sensitivity. The quenching constants of the complex toward Cu(II), Fe(III), Co(II), and TNP respectively are 8.6 × 104, 6.8 × 104, 6.5 × 104, and 2.1 × 105 M-1. The luminescent sensing of the nanowheel to metal cations is able to be explained by chelation enhancement of the quenching (CHEQ) effect, and its high selectivityto TNP is caused by the photoinduced electron transfer process and inner filter effect , even with the existence of other nitro-based explosives.

Full text of DOI:10.1021/acs.cgd.0c01742

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Article
High-Nuclearity Cd(II)−Nd(III) Nanowheel with NIR Emission Sensing
of Metal Cations and Nitro-Based Explosives
Yanan Ma, Xiaoping Yang,* Mengyu Niu, Wenxin Hao, Dongliang Shi, and Desmond Schipper
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ABSTRACT: One Cd−Nd nanowheel [Cd8Nd4L8(OAc)8]·4OH (1, molec-
ular sizes: 1.2 × 2.8 × 2.8 nm) was obtained by using one designed flexible
Schiff base ligand containing eight coordination sites. The Schiff base ligand
exhibits a hexadentate η1:η2:η1:η1:η2:η1:μ4 coordination mode. The chromo-
genic Cd/L components are able to transfer energy to Nd(III), leading to the
near-infrared (NIR) lanthanide emission of 1. The energy transfer efficiency
(ηsens) is calculated to be 39.4%. 1 shows interesting luminescent sensing
activity toward metal cations and nitro-based explosives, in particular to
Cu(II), Fe(III), Co(II), and 2,4,6-trinitrophenol (TNP) with high sensitivity.
The quenching constants of the complex toward Cu(II), Fe(III), Co(II), and
TNP respectively are 8.6 × 104, 6.8 × 104, 6.5 × 104, and 2.1 × 105 M−1. The
luminescent sensing of the nanowheel to metal cations is able to be explained
by chelation enhancement of the quenching (CHEQ) effect, and its high
selectivityto TNP is caused by the photoinduced electron transfer process and “inner filter effect”, even with the existence of other
nitro-based explosives.
very few reported wheel-like complexes containing large
organic ligands. Flexible ligands may show various coordina-
tion configurations to construct unusual frameworks.25,26
Recently, a {Gd18} nanowheel was constructed from a long-
chain diacylhydrazone ligand.27 Our research projects have
focused on the lanthanide-based nanoclusters with luminescent
sensing properties.28,29 Thus, with the designed salen-type
ligand 6,6′-((1E,1′E)-(((butane-1,4-diylbis(oxy))bis(2,1-
phenylene))bis(azaneylylidene))bis(methaneylylidene))bis(2-
methoxyphenol) (H2L, Scheme 1), a 12-metal Cd−Nd
nanowheel [Cd8Nd4L8(OAc)8]·4OH (1) was reported herein.
INTRODUCTION
■
The synthesis of wheel-like metal clusters has attracted much
interest during recent years due to fascinating geometrical
features as well as their interesting properties.1−4 The
combination of d-block metal and lanthanide ions may result
in high-nuclearity heterometallic clusters. Some nanoscale
metallo-rings based on d-block metals and lanthanides have
been constructed (e.g., Fe6Ln3,5 Co16Ln24,6 Cu36Ln24,7
Mn8Ln8,8 and Cu6(Zn6)Ln6 ). Giant d−f metal clusters often
9
exhibit interesting magnetic, electronic, and optic properties
due to their well-defined molecular units. So far, many reports
in wheel-like d−f metal clusters have focused on their potential
application in the field of magnetism, such as molecular
magnetism and magnetocaloric materials.5−9 However, lumi-
nescent wheel-like d−f clusters have received much less
attention. Recently, the development of fluorescent probes
based on lanthanides for the sensing of various analytes has
attracted growing attention since they may have potential
application in the protection of environment and biological
studies.10−14 Many luminescent lanthanide complexes and
metal−organic frameworks (MOFs) have been used in the
detection of small molecules and ions,15−20 while there are
very few reports on the luminescent probes so far by the use of
wheel-like d−f nanoclusters.
Scheme 1. Synthesis Route of Ligand H2L
Received: December 28, 2020
Revised: March 28, 2021
Published: April 14, 2021
A common way for the synthesis of wheel-like complexes is
to connect metastable self-assembled moieties into rings by the
use of simple polydentate organic ligands such as carbox-
ylates,5,7 phosphonates,21,22 and alkoxides,23,24 in order to get
single-molecule magnets (MCE). On the contrary, there are
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Dc = 1.063 g cm−3, μ(Mo Kα) = 0.992 mm−1, F(000) = 6360, GOF =
0.905, R1 = 0.0781, wR2 = 0.2049.
1 displays near-infrared (NIR) emission sensing of metal
cations and nitro-based explosives, in particular to Cu(II),
Fe(III), Co(II), and 2,4,6-trinitrophenol (TNP). As far as we
know, 1 is the first report of NIR luminescent sensor for the
detection of nitro-based explosives and metal cations by a
heterometallic d−f nanowheel.
RESULTS AND DISSCUSSION
■
Synthesis and Characterization. The H2L ligand was
obtained from the reactions with 1,4-dibromobutane, 2-
hydroxy-3-methoxybenzaldehyde, and 2-nitrophenol as start
EXPERIMENTAL SECTION
Synthesis of the Ligand H2L. See Scheme 1.
materials (Scheme 1) and was confirmed by 13C NMR, H
■
1
NMR, and ESI-MS (Figure S1 and S2). The yellow crystalline
product of 1 was produced by the reaction of H2L with
Cd(OAc)2 and Nd(SO3CF3)3. For the crystal data of 1, its
high R values are caused by the bad disorder of lattice solvent
molecules (i.e., MeOH and H2O), which is refined using the
platon squeeze technique. The centrosymmetric structure of
the complex has four equivalent Cd2Nd units connected by
Schiff base ligands (Figure 1). It has a diameter of 2.8 nm and a
central hole of 0.9 nm. The thickness of the wheel is 1.2 nm.
1,4-Bis(2-nitrophenoxy)butane. A 6.0 g amount of 4-nitro-
phenol (43.11 mmol) and 3.0 g of dry K2CO3 (21.55 mmol) were
dissolved in 25 mL of dry DMF. Then a 5 mL DMF solution of 1,4-
dibromobutane (4.17 g, 20.67 mmol) was added dropwise. The result
solution was heated to 115 °C overnight and then cooled on crushed
ice to give yellow solid. After the solid was filtered and successively
washed with water, ethanol, and diethyl ether, the solid product was
obtained. It was dried for 2 h under vacuum. Yield: 4.35 g (80%). 13C
NMR (DMSO-d6): 151.24, 139.55, 134.32, 124.80, 120.36, 115.03,
1
68.71, 24.98. H NMR (DMSO-d6): 7.86 (d, J = 8.00 Hz, 2H), 7.65
(t, J = 8.30 Hz, 2H), 7.26 (d, J = 8.60 Hz, 2H), 7.11 (t, J = 7.50 Hz,
2H), 4.24 (s, 4H), 1.91 (s, 4H). ESI-MS (positive, DMF): m/z =
332.10.
2,2′-(Butane-1,4-diylbis(oxy))dianiline. A mixture of 1,4-bis(2-
nitrophenoxy)butane (2 g, 6.02 mmol), Pd−C (0.5 g, 10%), and
hydrazine monohydrate (3 mL, 80%) in ethanol (30 mL) was heated
under a N2 atmosphere at 80 °C for 8 h. The resulting solution was
filtered to remove Pd−C and cooled to RT to yield a precipitate, and
then the solution was filtered and recrystallized using ethanol. The
solid product was dried under vacuum for 2 h. Yield: 1.20 g (72%).
13C NMR (DMSO-d6): 145.60, 137.75, 120.83, 116.20, 113.92,
1
111.77, 67.49, 25.70. H NMR (DMSO-d6): 6.78 (d, J = 8.10 Hz,
2H), 6.65 (m, J = 7.60 Hz, 4H), 6.50 (t, J = 7.50 Hz, 2H), 4.63 (s,
4H, N−H), 3.99 (s, 4H), 1.91 (s, 4H). ESI-MS (positive, DMF): m/z
= 272.15.
H2L. 2-Hydroxy-3-methoxybenzaldehyde (3.0430 g, 20.0 mmol)
was dissolved in EtOH (15 mL), and then a solution of 2,2′-(butane-
1,4-diylbis(oxy))dianiline (2.7215 g, 10.0 mmol) in EtOH (20 mL)
was added. The result solution was heated for 6 h with reflux and then
cooled to RT. The solid product was obtained by filtration, then
washed three times by 5 mL of EtOH, and dried under vacuum for 2
h. Yield (by 2,2′-(butane-1,4-diylbis(oxy))dianiline): 4.6415 g (91%).
1H NMR (CDCl3): 14.20 (s, 2H), 8.67 (s, 2H), 7.18 (d, J = 7.50 Hz,
2H), 6.92−6.98 (m, 8H), 6.83 (t, J = 7.00 Hz, 2H), 4.13 (s, 4H), 3.92
(s, 6H), 2.06 (s, 4H). 13C NMR (CDCl3): 161.82, 152.34, 148.73,
127.93, 124.58, 123.68, 120.80, 119.67, 119.57, 118.02, 114.58,
113.14, 68.43, 56.36, 26.20. ESI-MS (positive, CH2Cl2): m/z =
540.23.
Synthesis of [Cd8Nd4L8(OAc)8]·4OH (1). Triethylamine in
MeOH (1.0 mol/L, 1 mL) was added into the solution of 0.20
mmol of Nd(SO3CF3)3 (0.120 g), 0.04 mmol of Cd(OAc)2 (0.102 g),
and 0.20 mmol of H2L (0.110 g) in 9 mL of EtOH. The result
solution was heated under reflux for 30 min. The slow diffusion of
diethyl ether into the clear solution for 1 week produced the pale red
crystalline solid (0.0479 g, yield 35% by Nd(SO3CF3)3). Elemental
Anal. Found: C, 50.32; H, 4.50; N, 3.27. Calc for [Cd8Nd4L8(OAc)8]·
4OH·(MeOH)2(H2O)12: C, 49.78; H, 4.54; N, 3.39. Mp >270 °C
(dec). IR (CH3CN, cm−1): 3052 (w), 3008 (w), 2816 (w), 1608 (s),
1540 (s), 1440 (s), 1388 (m), 1328 (w), 1212 (s), 1164 (s), 1100 (s),
970 (s), 844 (m), 718 (s), 640 (m). ESI-MS (positive, CH3CN):
[CdNd2L3(HOAc)]2+ at m/z = 1035.0, [Nd2L(OAc)2 (OH)(H2O)]+
at m/z = 978.9.
Crystal Structure Determination. The diffraction data collec-
tion of 1 was performed on a Smart APEX CCD diffractometer with
Mo Kα radiation, and the crystal structure was determined by the
SHELX 97 program. For the structure of 1, the CCDC number is
2017378. The bond angles and lengths of the structure are exhibited
in Table S1.
Figure 1. Wheel-like structure of 1: (a) the coordination environ-
ments of metal cations in Cd2Nd moiety; (b) viewed from the c-axis;
(c) viewed from the a-axis. (Cd2+: green, Nd3+: blue).
For 1: C272H268Nd4Cd8O68N16, tetragonal (P4nc), a = 30.017(2) Å,
b = 30.017(2) Å, c = 21.935(3) Å, V = 19765(4) Å3, T = 190 K, Z = 2,
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Nd(III) ions are ten-coordinated with an irregular 3,4,4,4-
tetracapped trigonal prism coordination mode,30 while Cd(II)
ions show a distorted octahedral geometry. The neighboring
Cd(II) and Nd(III) ions are bridged by four O atoms from one
μ2-OAc− anion and two L2− ligands. The average Cd···Nd
distance is 3.711 Å. In 1, the Schiff base ligands were
deprotonated and display a hexadentate η1:η2:η1:η1:η2:η1:μ4
coordination mode. The bond lengths of Nd−O and Cd−O
are found to be 2.368−2.918 and 2.174−2.488 Å, respectively.
1 shows an open 3D channel-like structure by the linking of
Ar−H···π interactions (3.242−3.721 Å) (Figure 2a).31,32 For
Figure 3. Quenching of NIR luminescence of 1 (10 μM) aroused by
added Cu(II) in CH3CN (λex = 400 nm).
Figure 4. Quenching of NIR luminescence of 1 (10 μM) aroused by
added TNP in CH3CN (λex = 400 nm).
Figure 2. (a) 3D stacking structure viewed from the a-axis. (b) SEM
image. (c) EDX spectrum. (d) DLS analysis in CH3CN of 1.
instance, the emission of 1 is reduced about 50% upon the
addition of Cu(II), Fe(III), Co(II), and TNPsolutions with the
concentrations of 24, 30, 20, and 3.5 μM, respectively, while
the concentrations required for other metal cations and nitro-
based explosives to quench the emission of 1 by half are much
higher than these.
The NIR emission quenching constants (KSV) of the
complex to these metal cations and nitro-based explosives
were estimated by using the Stern−Volmer equation (Figures
5 and 6).40 The KSV values of 1 to Cu(II), Fe(III), Co(II), and
TNP are 8.6 × 104, 6.8 × 104, 6.5 × 104, and 2.1 × 105 M−1,
respectively. For 1, the limits of detection (LOD)41 to these
four analytes are calculated to be 1.3, 1.7, 1.8, and 0.55 μM,
respectively, demonstrating the high sensitivity toward them at
the ppm level. The KSV value of 1 to TNP is much higher than
the stacking structure of 1, its empty volume is estimated as
7238 Å3 by the PLATON program, which is about 37% of the
unit cell volume (19765 Å3). In the energy dispersive X-ray
spectroscopy of 1, the Cd/Nd molar ratio is confirmed to be
about 2 (Figure 2c). The ESI-MS spectrum of 1 shows the
presence of [Cd8Nd4L8(OAc)8]4+ at m/z = 1632.8 (Figure
S3). A narrow size distribution around 2.8 nm is found in the
dynamic light scattering analysis of 1 (Figure 2d), in agreement
with its crystal structure. These results display that, in solution,
1 maintains the cyclic structure, which is consistent with other
metallo-rings reported previously.33−37
Luminescent Response Behavior to Metal Cations
and Nitro-Based Explosives. The absorption spectrum of
the free H2L ligand shows intense bands at 280 and 338 nm,
which shift to 282 and 388 nm in 1 (Figure S7). 1 displays the
4
4
luminescence of Nd(III) (belong to F3/2 → Ij/2 transitions,
Figure S8), and the quantum yield (Φem) and luminescence
lifetime (τ) are found to be 1.3% and 8.19 μs, respectively
(Figure S9). Thus, the intrinsic quantum yield (ΦLn) of
Nd(III) and the efficiency (ηsens) of energy transfer from Schiff
bases to lanthanide ions are calculated to be 3.3% and 39.4%,
38
respectively, according to equations ΦLn = τ/τ0 and ηsens
=
Φem/ΦLn.39 To check the luminescent sensing properties of 1,
changes in the intensity at 1064 nm resulting from the addition
of metal cations and nitro-based explosives (Scheme S1) were
recorded. Interestingly, the added Cu(II), Fe(III), Co(II), and
TNP decrease the luminescence much faster than other
corresponding analytes (Figures 3, 4, S10, and S11). For
Figure 5. NIR emission quenching constants of 1 (10 μM) toward
different metal cations.
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Scheme 2. Energy Levels of HOMO and LUMO of the
Explosives
Figure 6. NIR emission quenching constants of 1 (10 μM) toward
different nitro explosives.
absorption at λex (400 nm). As shown in Figure 8, differing
from other explosives, TNP exhibits a much higher molar
those to other explosives. For instance, when the concentration
of add explosives is 15 μM, the luminescence quenching
percentage of 1 to TNP is more than 70%, which is much
higher than those to others (<10%) (Figure 7). Compared
with other explosives, TNP has more −NO2 groups, which is
able to help to form stronger intermolecular interaction with
the wheel-like cluster through hydrogen bonds.
Figure 8. Absorption spectra of explosives in CH3CN.
absorption at 400 nm (Figure 8), indicating that TNP is able
to compete with the Schiff base ligands in the complex for the
light energy and further decreases the lanthanide emission.
The selectivity of 1 to TNP was investigated through the
step-by-step addition of explosives (Figure 9). For example, the
Figure 7. NIR emission quenching percentages of 1 (10 μM) toward
nitro-based explosives (15 μM) (λex = 400 nm).
The emission sensing of 1 toward the metal cations may be
led by chelation enhancement of the quenching effect
(CHEQ), which may change the energy transfer efficiency in
the complex.42−44 For example, the addition of Cu(II), Fe(III),
and Co(II) may decreases the lanthanide emission by f → d
energy transfer,45,46 leading to the high KSV values of 1 to these
metal cations. The intermolecular interactions between the
nanowheel and metal cations play an important role in the
CHEQ effect. For example, electrostatic attractions can be
formed between the metal cations and the negative oxygen
atoms of 1. The UV−vis titrations display that the absorption
bands of the complex are blue-shifted or red-shifted with the
addition of Cu(II), Fe(III) and Co(II) ions (Figure S12),
indicating the formation of interactions between 1 and the
added metal cations. The origin of emission quenching of the
nanowheel aroused by the addition of nitro-based explosives
can be attributed to the photoinduced electron transfer
mechanism (PET), where the excited electrons of the Schiff
bases move to the LUMO orbitals of explosives.47−49
Compared with those of other explosives, the LUMO energy
level of TNP is much lower (Scheme 2), which is advantageous
to the acceptance of electron. Besides the PET process, the
emission quenching of 1 may also be aroused by the “inner
filter effect”,50 where the explosives show strong light
Figure 9. Decrease of emission intensities of 1 (10 μM) at 1064 nm
upon the step-by-step addition of nitro-based explosives (1 μM) in
CH3CN.
emission intensities of the complex at 1064 nm were not
reduced quickly when another nitro-based explosive (e.g., 1,3-
DNB) was added twice first; however, they were decreased
rapidly by the following addition of TNP with the same
concentration. This phenomenon repeats in the subsequent
cycles of the additions of 1,3-DNB and TNP. These results
suggest that the nanowheel has high selectivity toward TNP.
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https://pubs.acs.org/10.1021/acs.cgd.0c01742
CONCLUSIONS
■
Overall, a 12-metal Cd−Nd nanowheel 1 with a diameter of
2.8 nm was successfully obtained from one new Schiff base
ligand, which displays a hexadentate η1:η2:η1:η1:η2:η1:μ4
coordination mode. Interestingly, the nanowheel displays
NIR luminescent sensing behavior toward metal cations and
nitro-based explosives, in particular to Cu(II), Fe(III), Co(II),
and TNP at the ppm level. As far as we know, 1 is the first
report of a heterometallic d−f nanowheel for the NIR emission
sensing of metal cations and nitro-based explosives. The
luminescent sensing of the nanowheel toward the metal cations
is because of the CHEQ effect. The high selectivity of 1 to
TNP is due to the PET process and “inner filter effect”, and it
is not affected by other explosives.
Author Contributions
The manuscript was written by contributions of all authors. All
authors have given approval to the final version of the article.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully thank National Natural Science Foundation of
China (No. 21771141) and Key Foundation for High-level
Talents Innovation Technology Projects of Wenzhou (2019).
REFERENCES
■
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.cgd.0c01742.
■
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sı
General procedures; NMR, ESI-MS, IR, and UV−vis
spectra; TGA; powder XRD patterns; excitation, visible,
and NIR emission spectra; NIR emission lifetime;
chemical structures; NIR luminescent sensing; UV−vis
titrations; X-ray crystallography; and bond lengths
(PDF)
Accession Codes
CCDC 2017378 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
Corresponding Author
Xiaoping Yang − College of Chemistry and Materials
Engineering, Wenzhou University, Wenzhou 325035, China;
Zhejiang Key Laboratory of Carbon Materials, Wenzhou
325035, China; orcid.org/0000-0002-4370-517X;
Email: xpyang@wzu.edu.cn
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of toroidal magnetic moments in heterometallic 3d-4f metallocycles.
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(10) Cheng, T.; Hu, J.; Zhou, C.; Wang, Y.; Zhang, M. Luminescent
metal-organic frameworks for nitro explosives detection. Sci. China:
Chem. 2016, 59, 929−947.
Authors
Yanan Ma − College of Chemistry and Materials Engineering,
Wenzhou University, Wenzhou 325035, China; Zhejiang
Key Laboratory of Carbon Materials, Wenzhou 325035,
China
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Mengyu Niu − College of Chemistry and Materials
Engineering, Wenzhou University, Wenzhou 325035, China;
Zhejiang Key Laboratory of Carbon Materials, Wenzhou
325035, China
Wenxin Hao − College of Chemistry and Materials
Engineering, Wenzhou University, Wenzhou 325035, China;
Zhejiang Key Laboratory of Carbon Materials, Wenzhou
325035, China
Dongliang Shi − College of Chemistry and Materials
Engineering, Wenzhou University, Wenzhou 325035, China;
Zhejiang Key Laboratory of Carbon Materials, Wenzhou
325035, China
Desmond Schipper − Department of Chemistry and
Biochemistry, The University of Texas at Austin, Austin,
Texas 78712-0165, United States
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