Cluster-based CaII, MgII and CdII coordination polymers based on amino-functionalized tri-phenyl tetra-carboxylate: Bi-functional photo-luminescent sensing for Fe3+ and antibiotics

Article abstract of DOI:10.1016/j.dyepig.2019.107631

Excess and deficiency of iron(III) and antibiotics from normal permissible limits will induce serious disorders, so their detection is important but challenging. In this work, the asymmetric amino-functionalized tetra-carboxylate H₄L (2′-amino-1,1’:4′,1″-terphenyl-3,3″,5,5″-tetracarboxylic acid) containing large conjugated ter-phenyl aromatic backbones have been synthesized and employed. Through a one-pot powerful solvo-thermal synthetic strategy, a series of unique tri-nuclear cluster-based Ca^II, Mg^II and Cd^II coordination polymers, namely [Ca_1.5(μ₈-HL)(DMF)]_n (1), {[Mg_1.5(μ₇-HL)·(H₂O)₂]·3H₂O}_n (2) and {[Cd_1.5(μ₁₀-L)_0.75]_n·H₂O·DMF}_n (3) have been successfully prepared. 1–3 exhibit excellent photo-luminescent properties and good fluorescence stability. Structural analyses reveal that tri-nuclear Ca^II secondary building blocks (SBUS) are linked via HL^3?, forming the 2D clustered-based micro-porous coordination polymer 1. As for 2, three carboxylate groups of partly de-pronated HL^3? also link these neighboring tri-nuclear Mg^II SBUS, which constructs the 2D Mg^II coordination framework 2. As for 3, fully de-pronated L^4? also links these neighboring tri-nuclear Cd^II SBUS, which ultimately constructs the 3D micro-porous coordination framework 3. Experimental powder x-ray diffraction (PXRD) patterns coincide well with the theoretical patterns, which indicate that we have successfully synthesized the pure phase material 1–3. Photo-luminescent experiments demonstrate that coordination polymers 1–3 can be successfully applied towards bi-functional sensing for sensitive detection of Fe³⁺ and the antibiotics NZF (Nitrofurazone). To the best of our knowledge, this is the first example of the application of amino-functionalized tri-phenyl tetra-carboxylate based MOFs towards bi-functional discrimination of Fe³⁺ and NZF antibiotics with high efficiency K_sv values (For Fe³⁺: 7.28 × 10⁴ M^?1 for 1; 3.38 × 10⁴ M^?1 for 2 and 3.29 × 10⁴ M^?1 for 3 and for NZF antibiotics: 4.47 × 10³ M^?1 for 1; 4 × 10³ M^?1 for 2 and 5.6 × 10³ M^?1 for 3).

Full text of DOI:10.1016/j.dyepig.2019.107631

Accepted Manuscript
II
II
II
Cluster-based Ca , Mg and Cd coordination polymers based on amino-
functionalized tri-phenyl tetra-carboxylate: Bi-functional photo-luminescent sensing for
3+
Fe and antibiotics
Xin Shu Li, Jun Dan An, Hui Min Zhang, Jun Jie Liu, Yong Li, Gui Xiang Du, Xiang Xia
Wu, Ling Fei, Jed D. Lacoste, Zheng Cai, Yuan Yuan Liu, Jian Zhong Huo, Bin Ding
PII:
S0143-7208(19)30810-1
DOI:
https://doi.org/10.1016/j.dyepig.2019.107631
Article Number: 107631
Reference:
DYPI 107631
To appear in: Dyes and Pigments
Received Date: 13 April 2019
Revised Date: 30 May 2019
Accepted Date: 6 June 2019
Please cite this article as: Li XS, An JD, Zhang HM, Liu JJ, Li Y, Du GX, Wu XX, Fei L, Lacoste JD,
II
II
II
Cai Z, Liu YY, Huo JZ, Ding B, Cluster-based Ca , Mg and Cd coordination polymers based on
3+
amino-functionalized tri-phenyl tetra-carboxylate: Bi-functional photo-luminescent sensing for Fe and
antibiotics, Dyes and Pigments (2019), doi: https://doi.org/10.1016/j.dyepig.2019.107631.
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Cluster-Based CaII, MgII and CdII Coordination Polymers Based
On Amino-Functionalized Tri-Phenyl Tetra-Carboxylate:
Bi-Functional Photo-Luminescent Sensing for Fe3+ and
Antibiotics
Xin Shu Li a,c, Jun Dan An a,c, Hui Min Zhang a,c, Jun Jie Liua,c, Yong Lia,c, Gui Xiang
Dua,c, Xiang Xia Wu a,c, Ling Feid, Jed D Lacosted, Zheng Caib*, Yuan Yuan Liu a,c,
Jian Zhong Huo a,c and Bin Ding a,c*
aKey Laboratory of Inorganic-Organic Hybrid Functional Material Chemistry (Tianjin Normal
University), Ministry of Education, Tianjin Key Laboratoryof Structure and Performance for
Functional Molecule, College of Chemistry, Tianjin Normal University, 393 Binshui West Road,
Tianjin 300387, PR China
bSouthern Med Univ, Guangdong Prov Key Lab New Drug Screening, Sch Pharmaceut Sci,
Guangzhou 510515, Guangdong, Peoples R China
cKey Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Collaborative
Innovation Center of Chemical Science and Engineering (Tianjin), College of Chemistry, Nankai
University, Tianjin 300071, PR China
dChemical Engineering Department, University of Louisiana at Lafayette, Madison Hall, Room
218 C, Lafayette, LA 70504, United States
*To whom correspondence should be addressed.
E-mail:caizheng2002@sina.com; hxxydb@tjnu.edu.cn
Received Date (automatically inserted by publisher)
Abstract: Excess and deficiency of iron(III) and antibiotics from normal permissible
limits will induce serious disorders, so their detection is important but challenging. In
this work, the asymmetric amino-functionalized tetra-carboxylate H4L
(2’-amino-1,1’:4’,1’’-terphenyl-3,3’’,5,5’’-tetracarboxylic acid) containing large
conjugated ter-phenyl aromatic backbones have been synthesized and employed.
Through a one-pot powerful solvo-thermal synthetic strategy, a series of unique
tri-nuclear cluster-based CaII, MgII and CdII coordination polymers, namely
[Ca1.5(µ8-HL)(DMF)]n
(1),
{[Mg1.5(µ7-HL)·(H2O)2]·3H2O}n
(2)
and
{[Cd1.5(µ10-L)0.75]n·H2O·DMF}n (3) have been successfully prepared. 1-3 exhibit
excellent photo-luminescent properties and good fluorescence stability. Structural
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analyses reveal that tri-nuclear CaII secondary building blocks (SBUS) are linked via
HL3-, forming the 2D clustered-based micro-porous coordination polymer 1. As for 2,
three carboxylate groups of partly de-pronated HL3- also link these neighboring
tri-nuclear MgII SBUS, which constructs the 2D MgII coordination framework 2. As
for 3, fully de-pronated L4- also links these neighboring tri-nuclear CdII SBUS, which
ultimately constructs the 3D micro-porous coordination framework 3. Experimental
powder x-ray diffraction (PXRD) patterns coincide well with the theoretical patterns,
which indicate that we have successfully synthesized the pure phase material 1-3.
Photo-luminescent experiments demonstrate that coordination polymers 1-3 can be
successfully applied towards bi-functional sensing for sensitive detection of Fe3+ and
the antibiotics NZF (Nitrofurazone). To the best of our knowledge, this is the first
example of the application of amino-functionalized tri-phenyl tetra-carboxylate based
MOFs towards bi-functional discrimination of Fe3+ and NZF antibiotics with high
efficiency Ksv values (For Fe3+: 7.28×104 M-1 for 1; 3.38×104 M-1 for 2 and 3.29×
104 M-1 for 3 and for NZF antibiotics: 4.47×103 M-1 for 1; 4×103 M-1 for 2 and 5.6
×103 M-1 for 3).
Keywords: Amino-functionalized; Tetra-Carboxylate; Cluster-Based; Sensing; Fe3+;
Antibiotics
Introduction
With the development of modern industry, iron has been widely utilized;
furthermore Fe3+ ions are considered to widely exist in the biological system, playing
the crucial roles in many biochemical and physiological processes, such as DNA
replication, cellular life cycles, hemoglobin formation, electron transfer and et al.
[1-2]. When the amount of Fe3+ exceeds the normal concentrations, or if the amount
of Fe3+ drops in the biological systems, the result can give rise to serious diseases
such as methemoglobinemia, anemia and Alzheimer’s, which also can interfere with
metabolism and cellular homeostasis [3-6]. Thus, highly sensitive discrimination of
Fe3+ ions in aqueous environments is interesting and crucial for protecting human
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health.
Since Alexander Fleming discovered penicillin in 1929 [7], antibiotics have been
widely applied in the treatment of bacterial infections. Antibiotics have been
developed into very important kind of medicines. These antibiotics medications
widely exist in various fields such as aquacultures and biological systems, and can be
widely utilized for treating bacterial infections in humans and animals bodies. The
abuse of these medicines can give rise to an excessive concentration of antibiotics in
diverse water environments such as surface water, groundwater, wastewaters, and
even drinking water, especially in China [8]. Currently the detection methods for
antibiotics are usually limited due to sophisticated devices, high-cost, time consuming,
and complicated procedures. Among these methods are capillary electrophoresis,
surface enhanced Raman spectroscopy, liquid chromatography tandem mass
spectrometry and many more. [9-10]. Thus, the development of fast, cost-effective
and convenient detection methods for antibiotics in aqueous environments is
interesting and urgently needed.
In the recent thirty years, luminescent metal organic coordination frameworks
(MOFs) have been especially interesting [11-12], because they can be utilized for the
highly sensitive discrimination of different analytic objects such as environment
pollutants, biomarker molecules, volatile organic compounds, enzymes, proteins and
more [13-17]. These luminescent MOFs have tunable pore size, excellent structural
stability, and large surface areas. These advantages make these fluorescent
coordination materials have more competitiveness than other luminescent materials.
More analytical objects can effectively interact with the large, tunable, porous
surfaces of these fluorescent MOFs, which can enhance luminescent response,
decrease the detection limit values and improve the sensitivity [18].
For these luminescent MOFs-based sensors, aromatic poly-carboxylate ligands are
appealing and employed as bridging linkers because of their ideal rigid skeleton and
good chemical stability [19]. Especially the building blocks of ter-phenyl
poly-carboxylate, which have aroused great attention: (1) Ter-phenyl aromatic
backbones possess rich conjugated π-electrons, which facilitate good
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photo-luminescent properties of these materials; (2) Introduction of electronic-rich
aromatic ligands also has proven to be an efficient strategy to enhance
photo-luminescent sensing properties of these coordination materials [20]; (3) -NH2
functional group is interesting and has received great attention. For example, it is
noted that the -NH2 functional group can be introduced into the coordination material
and effectively tune framework properties such as gas absorption/separation and
catalytic properties [21]. However, to date, luminescent MOFs-based sensors based
on asymmetric amino-functionalized tri-phenyl tetra-carboxylate are not reported
[22].
We are interested in the construction of these coordination polymers possessing
unique functional applications and beautiful architectures [23]. In this work,
amino-functionalized tri-phenyl tetra-carboxylate H4L (2’-amino-1,1’:4’,1’’-
terphenyl-3,3’’,5,5’’-tetracarboxylic acid) containing large conjugated ter-phenyl
moieties have been utilized (Scheme 1 and Scheme 2). Based on H4L, through
one-pot powerful solvo-thermal synthetic strategy, a series of unique tri-nuclear
cluster-based
[Ca1.5(µ8-HL)(DMF)]n
CaII,
MgII
and
CdII
coordination
polymers,
(2)
namely
and
(1),
{[Mg1.5(µ7-HL)·(H2O)2]·3H2O}n
{[Cd1.5(µ10-L)0.75]n·H2O·DMF}n (3) have been successfully prepared. PXRD patterns
have been determined, and clearly indicate pure phases of coordination polymers 1-3.
Photo-luminescence investigations suggested that 1-3 can be applied as the first
example of bi-functional MOFs-based fluorescent probes for trace amounts of Fe3+
and antibiotics NZF.
Experiment Section
General remarks: Amino-functionalized tri-phenyl tetra-carboxylate ligand H4L can
be prepared according to the previous reported procedures [24], which is also listed in
the supporting material (Fig. S1). Deionized water has been utilized as the solvent. All
the other chemical regents can be commercially purchased and utilized without
additional purification. A Perkin-Elmer 240 elemental analyzer is utilized for
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elemental microanalyses of C, H and N. A Rigaku D/Max-2500 X-ray diffractometer
apparatus equipped with Cu-Kα radiation is utilized for Powder X-ray diffraction
characterization of 1-3. An NETZSCH TG 209 apparatus with a 10 °C min-1 heating
rate is utilized for thermogravimetric analysis. PerkinElmer Lambda 35
spectrophotometer was utilized to recording UV-vis adsorption spectra.
Photo-luminescent lifetime and quantum yield were performed using a FS5
Fluorescence Spectrometer (Edinburgh).
A
Cary Eclipse Fluorescence
spectrophotometer (Agilent Technologies) is utilized for photo-luminescence sensing
experiments, and is equipped with a plotter unit and a quartz cell (1 cm × 1 cm) in the
phosphorescence mode.
Preparation of [Ca1.5(µ8-HL)(DMF)]n (1): Ca(NO3)2·4H2O (141.6 mg, 0.6 mmol)
and H4L (42.1 mg, 0.1 mmol) were mixed and stirred for 0.5 h in water (2 mL) and
DMF (6 mL), then HNO3 (5 µL, 0.33 M) was added. Then the mixed solutions were
put into a Teflon vessel in a steel autoclave. The temperature of steel autoclave is
programmatic controlled to be heated to 90 oC for 0.5 hour and kept at 90 oC for 72
h, then cooled down to ambient temperature during the period of 48 h. The obtained
colorless block-shaped crystals were cleansed several times by water and diethyl ether.
Yield: 36 % based on H4L. Elemental analysis calculations (%) for C25H19Ca1.5N2O9:
C 54.44, H 3.47, N 5.07; found: C 54.89, H 3.76, N 5.67. FT-IR data (cm-1): 3347(bm),
1715(m), 1611(w), 1648(w), 1569(w), 1385(s), 1225(m), 1137(w), 1106(m), 779(s),
732(s), 678(s).
Preparation of {[Mg1.5(µ7-HL)·(H2O)2]·3H2O}n (2): MgCl2·6H2O (61.0 mg, 0.3
mmol) and H4L (42.1 mg, 0.1 mmol) were mixed and stirred for 0.5 h in water (2 mL)
and DMF (6 mL), then HNO3 (5 µL, 0.33 M) was added. Then the mixed solutions
were put into a Teflon vessel in a steel autoclave. The temperature of steel
autoclave is programmatic controlled to be heated to 90 oC for 0.5 hour and kept at
o
90 C for 96 h, then cooled down to ambient temperature during the period of 48 h.
The obtained colorless block-shaped crystals were cleansed several times by water
and diethyl ether. Yield: 49 % based on H4L. Elemental analysis calculations (%) for
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C22H22Mg1.5NO13: C 48.50, H 4.07, N 2.57; found: C 49.11, H 3.71, N 2.89. FT-IR
data (cm-1): 3314(bs), 1715(w), 1630(s), 1540(s), 1480(s), 1251(w), 1104(w), 795(m),
740(m), 725(m), 663(w).
Preparation of {[Cd1.5(µ10-L)0.75]n·H2O·DMF}n (3): CdCl2·2.5H2O (68.5 mg, 0.3
mmol) and H4L (42.1 mg, 0.1 mmol) were mixed and stirred for 0.5 h in water (2 mL)
and DMF (6 mL), then HNO3 (5 µL, 0.33 M) was added. Then the mixed solutions
were put into a Teflon vessel in a steel autoclave. The temperature of steel
autoclave is programmatic controlled to be heated to 90 oC for 0.5 hour and kept at
o
90 C for 72 h, then cooled to ambient temperature during the period of 48 h. The
obtained colorless block-shaped crystals can be cleansed several times by water and
diethyl ether. Yield: 36 % based on H4L. Elemental analysis calculations (%) for
C19.5H16.5Cd1.5N1.75O8: C 40.95, H 2.91, N 4.29; found: C 41.17, H 2.67, N 3.71.
FT-IR data (cm-1): 3408(br), 1660(m), 1615(m), 1612(m), 1578(s), 1446(m), 1369(s),
1252(w), 1101(m), 778(s), 751(m), 725 (s).
X-ray Crystallography. Bruker SMART 1000 CCD diffractometer apparatus is
equipped with graphite-monochromatic Cu-Kα radiation (λ = 1.54184 Å), which is
utilized to determine single crystal diffraction intensities for 1-3. A ω-φ scanning
strategy was utilized adopting Lorentz polarization and absorption corrections. Direct
methods are utilized to refine the structures of 1-3. Full-matrix least-squares
techniques utilizing the SHELXL-2014 program are also applied to refine the
structure. Aromatic ring hydrogen atoms were allocated geometrically, isotropic
thermal parameters of these hydrogen atoms are 1.2 times than those hydrogen atoms
attached to carbon atoms. Guest solvent molecules are highly disordered and cannot
be precisely allocated utilizing X-ray crystallography, the SQUEEZE strategy has
been utilized to remove these guest solvent molecules in the void spaces [25].
Additionally, guest solvent molecules can be further analyzed by elemental analysis
and thermal analysis. CCDC-1859883 (1), CCDC-1859892 (2), CCDC-1870694 (3)
represent the supplementary crystallographic data for this work. These crystal data
can be downloaded free of charge from Cambridge’s Crystallographic Data Centre via
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the website www.ccdc.cam.ac.uk/data_request/cif. Crystallographic data and
refinement details for 1-3 are summarized in Table 1. Selected bond lengths and
angles of 1-3 are listed in Table S1.
Results and Discussion
Structural descriptions of coordination polymers 1-3 Crystal X-ray diffraction
characterization results reveal that the fundamental structural unit of complex 1
contains a 1.5 CaII center (Ca2 and 0.5 Ca1), one partially de-pronated HL3- and one
coordinated DMF molecule (Fig. 1). Ca1 is six-coordinated by six O atoms (O1A,
O1B, O3A, O3B, O5B, O5A) from HL3-, while Ca2 is six-coordinated by five oxygen
atom (O1A, O2A, O3A, O4A, O6 and O9) from HL3- carboxylate groups and one
oxygen atom (O9) from the terminally coordinated DMF. Ca1, Ca2 and Ca2A are
inter-linked through oxygen atoms of carboxylate groups generating tri-nuclear Ca3O4
clusters as secondary cluster-based building blocks (SBUS).
Its three carboxylate groups of each HL3- ligand also link three neighboring
tri-nuclear Ca3O4 SBUS adopting the bridging multi-dentate coordination mode,
which ultimately forms the 2D clustered-based micro-porous coordination material 1
(Fig. 2). Neighboring tri-nuclear CaII cluster separations are 9.962(1) Å and 14.843(1)
Å (For 1), which also can be observed through the crystallographic a-axis. A
one-dimensional channel with dimensionality of 4.978(1) Å × 6.568(6) Å can be
observed in the packing architecture of 1 viewed along the crystallographic a axis
(Fig. S2). The porous percentage in MOF 1 were calculated by Platon program, the
calculated results were 1131.8 Å, ca 19.0 % free solvent molecules can be accessible
to the void in 1 (5957.3Å3). On the other hand, coordinated oxygen atoms from HL3-,
DMF carbon and DMF oxygen atoms were involved into C-H···O hydrogen bonds
(C(23)-H(23)···O(3), 3.148(1) Å; C(25)-H(25A)-O(9), 2.785(8) Å). Such hydrogen
bonding interactions also play an important role in stabilizing the whole coordination
network of 1.
As for the coordination material 2, structural analysis reveals that the
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fundamental structural unit contains a 1.5 MgII center (Mg1 and 0.5 Mg2), one
partially de-pronated HL3- and two coordinated water molecules (Fig. 3). Mg1 is
six-coordinated by four oxygen atoms (O1, O5A, O6A, O7A) from HL3- and two
oxygen atoms (O9, O10) from two coordinated H2O molecules. While Mg2 is
six-coordinated by six carboxylate oxygen atoms (O2, O2A, O5A, O5B, O8A and
O8B) from HL3-. Mg1, Mg2 and Mg1A are linked via carboxylate oxygen atoms
forming tri-nuclear Mg3O4 clusters as secondary cluster-based building blocks
(SBUS).
Its three carboxylate groups of each HL3- ligand also link three neighboring
tri-nuclear MgII SBUS adopting a multi-dentate bridging mode, which ultimately
forms the 2D clustered-based micro-porous coordination material 2 (Fig. 4).
Neighboring tri-nuclear MgII cluster separations are 9.557(1) Å and 14.80(1) Å (For 2)
can be observed through the crystallographic a axis. One-dimensional micro-porous
channels can be observed in the packing architecture of 2 viewed along the
crystallographic a axis. The porous percentage in MOF 2 were calculated by the
Platon program, the calculated results were 2552.8 Å, ca 39.9 % solvent accessible
void in 2 (6392.9 Å3). On the other hand, coordinated oxygen atoms from HL3-,
coordinated water oxygen atoms were involved into N-H···O and O-H···O hydrogen
bonds (N(1)-H(1B)···O(1), 3.052(5) Å; O(9)-H(9B)-O(4), 2.662(7) Å;
O(10)-H(10A)-O(4), 2.715(9) Å). Such hydrogen bonding interactions also play an
important role in stabilizing the 2D micro-porous network of 2.
As for coordination material 3, structural analysis reveals that the fundamental
structural unit contains 1.5 CdII center (Cd1 and 0.5 Cd2) and 0.75 full de-pronated
L4- (Fig. 5). Cd1 is seven-coordinated by seven oxygen atoms (O1, O3A, O4A, O5B,
O5C, O6B, O6C) from L4- carboxylate groups, while Cd2 is six-coordinated by six
oxygen atoms (O2, O2A, O5B, O5C, O5D, O5E) from carboxylate groups of L4-. Cd1,
Cd2 and Cd1A are linked via carboxylate oxygen atoms forming tri-nuclear Mg3O4
clusters as secondary cluster-based building blocks (SBUS).
Four carboxylate groups of each L4- also link these neighboring tri-nuclear CdII
SBUS adopting multi-dentate coordination mode, which ultimately forms the 3D
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clustered-based micro-porous coordination material 3 (Fig. S3). Neighboring
tri-nuclear CdII cluster separations are 9.889(1) Å, 10.464(1) Å and 14.90(1) Å (For 3)
can be observed, respectively. One-dimensional micro-porous channels with
dimensionality of 6.718(8) Å × 6.648(6) Å can be observed in the packing
architecture of 3 viewed along the crystallographic b axis. The porous percentage in
MOF 3 were calculated by Platon program, the calculated results were 997.9 Å, ca
35.8 %solvent accessible void in 3 (2785.1 Å3).
PXRD, FT-IR, Thermal stabilities and Photo-luminescent properties of
coordination polymers 1-3 Powder X-ray diffraction (PXRD) patterns have been
determined for the crystalline materials of 1-3. As shown in Fig. 6, both peaks
position and lines sharpness of experiment PXRD patterns are consistent with these
simulated theoretical PXRD patterns based on crystal X-ray data. The result also
unambiguously reveals that these corresponding as-synthesized samples have the
same structures to that that of X-ray crystal data [26-27]. The slight dissimilarities in
reflection intensities should be correlated with the crystal orientation difference of
powder samples [28]. As for coordination material 3, varied-temperature powder
X-Ray patterns for the highly-dimensional CdII coordination framework also has been
made. As exhibited in Fig. 7, structure of 3 can remain stable up to 150 oC indicating
the coordination material 3 has good thermal stability.
Thermogravimetric decay analysis (TGA) curves of coordination materials 1-3
o
also have been determined (Fig. S4). As for 1, the weight loss varying from 30 C to
o
250 C are 12.6 %, which should be correlated with the weight loss for one
coordination DMF. As for 2, the weight loss varying from 30 oC to 150 oC are 16.3 %
(calcd 16.5 %), which should be correlated with the weight loss for two coordination
o
water and three lattice water molecules. As for 3, the weight loss varying from 30 C
to 250 oC are 15.1 % (calcd 15.9 %), which should be correlated with the weight loss
for one free water and one free DMF [29]. As for 1-3, the weight loss from 250 oC to
800 oC should correspond for the framework collapse of these coordination polymers.
The remaining residue at 800 oC should correspond for the metal oxide.
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FT-IR spectra of coordination polymers 1-3 also have been determined, these
representative absorption bands for solvent and the building blocks of HL3- or L4- can
be observed. As for 1-3, broad and medium bands centered at ca. 3400 cm-1 can be
observed, which can be correlated with the typical characteristic band of coordinated
and free water or DMF in the coordination network. The absence of strong peaks
located at ca. 1700 cm-1 demonstrates complete de-protonated carboxylic groups of
L4- in 3. For 1-3, the symmetric and asymmetric stretching vibrations for carboxylate
groups are located in the ranges of 1369-1480 and 1540-1662 cm-1, respectively,
which is consistent with previous literature results [30]. All the FT-IR typical
absorption bands and thermogravimetric analyses are well consistent with single
crystal X-ray result of coordination polymers 1-3.
It is well known that coordination polymers can effectively tune their emission
wavelengths and strengths through rational incorporation of different conjugated
aromatic building blocks. Through introduction of diverse conjugated aromatic
organic linkers and metal centers such as 2p, 3d and 4f, the synthetic strategy is
efficient for preparing unique photo-luminescent materials [31]. Because H4L
contains large ter-phenyl rigid backbones, it is anticipated to generate excellent
photo-luminescent emissions. Therefore, we are greatly interested to determine
photo-luminescent properties of H4L and coordination polymers 1-3, respectively.
As exhibited in Fig. S6, at the room temperature, the amino-functionalized
tri-phenyl tetra-carboxylate building block has strong photo-luminescent emissions in
water solutions, with a maximum located at 398 nm for free H4L (λex = 330 nm). The
strong photo-luminescent band of H4L also facilitate that the coordination polymers
1-3 can be applied in the photo-luminescent detection. For H4L, the
photo-luminescent emissions can be correlated with conjugated ter-phenyl
chromospheres, therefore the corresponding bands can be defined as π-π* transition
emission. When the crystalline materials of 1-3 were ground into powder samples and
suspended into the water solutions, the 2D and 3D metal-organic materials 1-3 also
exhibit the strong luminescent emission peaks (maximum peak location: for 1: 403
nm; for 2: 402 nm; for 3: 400 nm upon excitation at 300 nm). In comparison with that
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of free H4L, these emissions of 1-3 can be ascribed to intra-ligand photo-luminescent
emissions because similar photo-luminescent bands can be found for the
amino-functionalized tri-phenyl tetra-carboxylate H4L in the aqueous solutions [32].
On the other hand, a shoulder emission of 1 at 450 nm also can be observed, which is
red-shifted than that of free H4L and may be ascribed to ligand to metal charge
transfer (MCLT). As illustrated in the previous review literature [33], charge-transfer
luminescence are often observed in MOFs, LMCT/MLCT luminescence can also
compete with ligand-based luminescence, which can result in both LMCT/MLCT and
ligand-based emission bands. Further the completion between LMCT and
ligand-based emission bands may make that the intensity of ligand-based band
centered at 400 nm is slightly weaker than that of free H4L.
Photo-luminescent quantum and the lifetime of cluster-based coordination
compounds 1-3 also have been determined. The quantum yield is 12.23 % for 1,
10.89 % for 2 and 8.94 % for 3, which is good and can be correlated with large
ter-phenyl conjugated aromatic systems. The result can be compared with the
previously reported coordination polymers [34]. On the other, the lifetime of
luster-based coordination compounds also has been determined indicating 5.35 ns for
1, 4.75 ns for 2 and 3.16 ns for 3 (Fig. S12 and Table S3). Such result also can be
compared with recently reported zinc(II) coordination probes (3.71 ns) [35].
Photo-luminescent sensing for Fe3+ by Cluster-Based CaII, MgII and CdII
Coordination Polymers 1-3. Inorganic-organic hybrid coordination materials have
aroused great attention because of their tunable fluorescent emissions and broad
application prospects as photo-luminescent materials. Because these materials can
deliberately change their emission strengths and wavelengths, the synthesis of
coordination materials can be tuned through judiciously selecting diverse organic
building blocks and central metal ions/clusters, which is quite important for obtaining
these new photo-luminescent coordination materials.
In this work, the fluorescent properties of H4L and materials 1-3 based on H4L in
water solutions have been investigated. Furthermore, the aqueous stability of
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coordination polymers 1-3 was also characterized. The solid-state samples of
coordination materials 1-3 were suspended into the aqueous solutions for 12 h, then
filtered, the resulting solid state samples were then dried by the vacuum oven. These
obtained solid state samples were analyzed by PXRD patterns. The PXRD patterns of
1-3 after suspending in the aqueous solutions for 12 hours still are consistent with
theoretical PXRD patterns based on single-crystal X-ray data. The result reveals that
structures of coordination polymers 1-3 remain unchanged in the aqueous solutions.
On the other hand, the photo-luminescent peaks are almost unchanged, indicating
coordination polymers 1-3 have good fluorescent stability for at least 12 h. The good
photo-luminescent stability may be ascribed to good solvent dispersibility and
stability of coordination materials 1-3 in the aqueous solutions. Therefore,
coordination materials 1-3 may be considered as good candidates as fluorescent
probes in aqueous solutions.
The solid-state samples of coordination polymers 1-3 were then tested for the
sensing of diverse metal ions. In order to investigate diverse photo-luminescent
responses to metal ions, the crystalline materials of 1-3 were ground into powder
samples, these samples are suspended into the water solutions of the same
concentration (60 µM) containing diverse metal chloride salt (Na+, Ca2+, Sr2+, NH4 ，
+
K+, Mg2+, Zn2+, Cd2+, Mn2+, Ni2+, Co2+, Ag+, Fe2+, Cu2+, Fe3+) in neutral conditions.
As shown in Fig. 8 and Fig. 9(a), Fe3+ exhibits a significant fluorescent quenching
effect, while other metal ions only have a slight effect. Because Al3+ can also partially
quench the signal, therefore the ksv value is also compared in 1 (Fig. S11 (a)), the
Ksv[Fe(III)]/Ksv[Al(III)] comparison value is 6.69, such value can be compared with
the comparison value in the recently reported Cd(II)-organic frameworks with
chelating NH2 sites for selective detection of Fe(III) [36]. Further we also compare the
emission spectra intensity of 1 dispersed in water suspensions upon addition of Fe(III)
ions (30µM), simultaneous addition of Fe(III) ions (30µM) and some other metal
cations (150 µM) (Fig. S11(b)), which also indicate selective sensing for Fe(III).
PXRD patterns for 1-Fe3+, 2-Fe3+ or 3-Fe3+ were also characterized and are consistent
with theoretical PXRD patterns based on crystal structures, revealing that
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coordination structures of micro-porous materials 1-3 remain unchanged. The result
demonstrates coordination polymers 1-3 have highly selective discrimination of Fe3+
in aqueous solutions. Thus, coordination polymers 1-3 should be utilized as the ideal
coordination probe materials for selective photo-luminescent detection of Fe3+ ions.
In order to investigate photo-luminescent detection limit of 1 as a fluorescent
probe for Fe3+, as shown in Fig. 9(b), a series of suspensions of 1-Fe3+ (3 µM to 286.2
µM) in water solutions have been synthesized by adding diverse concentrations of
Fe3+ into the water solutions containing the suspension of coordination material 1. It is
noted that when the concentrations of Fe3+ gradually increase, the photo-luminescent
intensity of 1 gradually decreases. As shown in Fig. 9(c), photo-luminescent intensity
has a liner correlation with concentration when the concentrations of Fe3+ changes
from 3 µM to 286.2 µM. The photo-luminescent detection limit of 1 for Fe3+ can be
calculated using the below equation: detection limit = 3σ/k (where k is the slope
between the fluorescent intensity vs. log Fe3+ at lower concentration; σ is the standard
deviation of blank determination) [37]. To characterize the correlation between Fe3+
concentration and quenching results, the linear fit plot of photo-luminescent intensity
vs. Fe3+ concentration was also made (Fig. 9(d)), which can be fitted through the
equation I0/I = 1 + Ksv[Fe3+] (I0 and I are the photo-luminescent intensities of 1 before
and after adding Fe3+, respectively; Ksv is the photo-luminescent quenching rate
constant; and [Fe3+] is the concentration of Fe3+). The Ksv value is calculated to be
7.28×104 L·mol-1 and low detection limit (5.91 × 10-6 M (S/N = 3)) demonstrating
high photo-luminescent quenching efficiency for Fe3+ based on the emissions of
coordination material 1. Additionally, as listed in Fig. 10 and Table S2, Ksv values are
calculated to be 3.38 × 104 L·mol-1 for 2 and 3.29 × 104 L·mol-1 for 3, which also
indicate high quenching efficiency of Fe3+ through the photo-luminescent emissions
of coordination materials 2-3 (Fig. S9).
To understand the photo-luminescent sensing mechanism of the fluorescence
quenching effect of coordination materials 1-3 toward Fe3+, further experiments were
carried out. As for coordination materials 1-3, the investigations were listed as follows:
(1) PXRD patterns of samples after photo-luminescent quenching is also compared
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and almost identical with that of the as-synthesized powder samples, which indicate
coordination materials 1-3 are still stable in the detection process (Fig. S8); (2) The
lifetime of fluorescence is an important parameter in judging the mechanism of
fluorescence quenching, which can often reflect whether the quenching effect is based
on a static or a dynamic mechanism [38]. As shown in Fig. S12 and Table S3, when
Fe3+ is added, the luminescence lifetimes of 1-3 gradually decrease, indicating the
existence of dynamic quenching mechanism. As described in the recently reported
lanthanide chemosensor [La(TPT)(DMSO)2]·H2O (H3TPT = p-terphenyl-3,4’’,5-
tricarboxylic acid) [39], such dynamic quenching mechanism can be governed by the
diffusive collisions between the electron-deficient Fe3+ and the terphenyl moieties of
H4L; (3) on the other hand, as demonstrated in the Stern-Volmer plot of 1 (Fig. 9(d)),
there is a non-linear and upward curvature at higher concentrations of Fe3+ ions,
suggesting the static quenching mechanism (namely the formation of ground-state
non-fluorescent complex between Fe3+ and coordination frameworks) also exist.
Cycle performance for detection of Fe3+ is also explored, however no good cycle
performance can be observed, which also behave the existence of the interactions
between Fe3+ and coordination compounds. Generally the NH2- group in luminescent
materials can be regarded as an electron-donating group and suitable for binding the
electron accepting metal ions, which may be important in the interaction with Fe3+.
For example, the luminescent Cd(II)-organic frameworks with chelating NH2 sites
also behave highly sensitive and selective detection of Fe(III) [36]. Overall, the
combination of dynamic and static quenching mechanism may be important for
fluorescence quenching effect towards Fe(III).
It is also noted that the shoulder peak at about 450 nm increased with increasing
the concentration of Fe3+. Because the shoulder band centered at 450 nm also is
observed in these coordination polymers, which can be assigned as ligand to metal
transfer (LMCT). Therefore when LMCT and ligand-based emission bands co-exist
and compete in the coordination polymers, if the ligand-based emission bands
gradually decrease, the band center at about 450 nm based on LMCT may gradually
increase.
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In comparison with the heavy metal ions Cd2+ in 3, Fe3+is not so toxic, therefore
the detection of Fe3+ by the non-toxic alkali CaII and MgII metal coordination
polymers 1 and 2 should be more meaningful and advantageous in the detection
process. As far as we know, work on these CaII and MgII coordination materials as
photo-luminescent probes for discriminating and sensitively detecting Fe3+ is still
scarcely reported [40-42]. The experiments demonstrated that coordination materials
1-3 represent the scarcely reported example of amino-functionalized tri-phenyl
tetra-carboxylate MOFs-based probes for detecting Fe3+ with high selectivity and high
sensitivity [43-44].
Chemosensor for antibiotics by Cluster-Based CaII, MgII and CdII Coordination
Polymers 1-3. Nowadays antibiotics have been widely utilized for treating bacterial
infections in humans and animals bodies. However when these medicines containing
antibiotics is overused, they can become a class of organic pollutants in the natural
water environments. Thus, rapid discrimination of antibiotics in water environments is
of great importance considering that overuse of antibiotics may be harmful to human
health and environmental protection. Considering the good photo-luminescence
behaviors and high porosities of coordination materials 1-3, it will be interested to
utilize them as potential fluorescent sensors for detecting antibiotics such as
Nitrofurantoin (NFT), Furazolidone (FZD), Nitrofurazone (NZF), Ornidazole (ORN),
Ronidazole (RNZ), Dimetridazole (DMZ), Metronidazole (MDZ), Sulfamethazine
(SMZ), Sulfadiazine (SDZ), Thiamphenicol (THI) and Chloramphenicol (CHL). To
explore the ability of 1-3 to detect a trace quantity of antibiotics, photo-luminescent
experiment were made by gradually adding antibiotics into water suspensions of
coordination polymers 1, 2 and 3. During the titration experiments, the samples of
coordination polymers 1, 2 or 3 were added into water solutions (2.5 mL), and then a
selected antibiotics are subsequently added forming the aqueous solutions containing
different antibiotics (180 µM). The fluorescence quenching percentage in terms of a
certain amount of different antibiotics at ambient temperature is demonstrated in Fig.
11. Obviously, the sensing experiments show high photo-luminescent quenching of
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coordination materials 1-3 occurs upon the addition of different antibiotics, and the
order
of
quenching
efficiency
is
NZF>NFT>MDZ>DMZ>RNZ>SMZ>CHL>ORN>FZD>SDZ>THI
for
1,
NZF>NFT>MDZ>RNZ>DMZ>SMZ>CHL>ORN>FZD>SDZ>THI for 2, and
NZF>NFT>MDZ>DMZ> RNZ>SMZ>CHL>FZD>ORN>SDZ>THI for 3. It is also
noted that coordination polymers 1, 2 and 3 have the highest quenching efficiencies
toward NZF (Nitrofurazone).
Furthermore, the fluorescence intensity vs. NZF antibiotics plot is also made
according to the Stern-Volmer equation. The SV plots for NZF are nearly linear in the
concentration ranges varying from 0 to 2.4 mM. Based on the experimental data
exhibited in Fig.12 and Fig. S10 in the ESI, the Ksv of coordination polymers 1-3 are
calculated to be 4.47×103 M-1 (for 1), 4×103 M-1 (for 2) and 5.6×103 M-1 (for 3). The
detection limits of 1, 2 and 3 toward NZF were 9.61 × 10-5 M (for 1), 1.86 × 10-4 M
(for 2) and 7.67 × 10-5 M (for 3), respectively (Tables S2 in the ESI†). Such high Ksv
values and low detection limits are comparable to the value for the reported
Zr(IV)-MOFs.
As for the sensing mechanism of NZF, further experiments including PXRD
pattern, fluorescence lifetime and UV-visible absorption spectra were carried out. The
investigations were listed as follows: (1) PXRD patterns of samples 1-3 after
photo-luminescent quenching is also compared and almost identical with that of the
as-synthesized powder samples, which indicate cluster-based coordination polymers
1-3 are still stable in the detection process (Fig. S8); (2) The luminescence lifetimes
of 1-3 in the absence or presence of NFs are almost the same (Fig. S12 and Table S3),
indicating that there is no significant interactions between these coordination
polymers 1-3 and the NZF analytes [45-51]; (3) UV-vis absorption spectra of NFs
exhibit the overlap with the excitation spectrum of 1-3 between 300 and 450 nm (Fig.
S
5), there should exist a competitive absorption for the light source energy between
1-3 and NFs; (4) On the other hand, we also examine the cycling performance for
detecting NZF antibiotics. As shown in Fig. S7, it can be observed partial
photo-luminescent recovery can be accomplished through simple washing these
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suspended powders by water, which also indicates there should not strong
coordination interactions between coordination polymers 1-3 and NZF; (5) It is also
noted that the shoulder peak at about 450 nm also increased with increasing the
concentration of antibiotics. A possible reason is that when LMCT and ligand-based
emission bands co-exist and compete in the coordination polymers, if the ligand-based
emission bands gradually decrease, the band center at about 450 nm based on LMCT
may gradually increase, which also exhibit the existence of photo-luminescent energy
transfer (PET) mechanism.
As a result, the photo-luminescent energy transfer (PET) mechanism enables
NZF to have a high photoluminescence quenching effect compared with other studied
antibiotics. Similar energy transfer mechanism can be observed in the recently
reported sodium(I)–europium(III)-organic sensor for nitrofuran antibiotics detection
[52]. However, as far as we know, this represents the first example for
photo-luminescent probes for NZF antibiotics utilizing amino-functionalized
tri-phenyl tetra-carboxylate based cluster-based coordination polymers 1-3.
Conclusions and Perspectives
When modern chemical industry is developed in the high-speed model, iron and
antibiotics has been widely utilized. Scientists also gradually realized that Fe3+
and antibiotics have the important applications in the biochemical processes and
medicinal cure. Thus, the development of new sensing materials to detect Fe3+ and
antibiotics from the water environment is quite important. In this work
amino-functionalized
tri-phenyl
tetra-carboxylate
H4L
(2’-amino-1,1’:4’,1’’-terphenyl-3,3’’,5,5’’- tetracarboxylic acid) have been employed.
A series of unique tri-nuclear cluster-based CaII, MgII and CdII coordination polymers,
namely {[Ca1.5(µ5-HL)·(DMF)}n (1), [Mg1.5(µ7-HL)·(H2O)2]n (2) and [Cd3(µ10-L)1.5]n
(3) have been isolated under the powerful solvo-thermal methods. Structural analyses
reveal that 1 contains tri-nuclear CaII secondary building blocks (SBUS), which are
further linked via HL3- forming the 2D clustered-based micro-porous coordination
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polymer 1. As for 2, three carboxylate groups of partly de-pronated HL3- link these
neighboring tri-nuclear MgII SBUS, which constructs the 2D MgII clustered-based
coordination material 2. As for 3, four carboxylate groups of fully de-pronated L4-
also link these neighboring tri-nuclear CdII SBUS, which ultimately constructs the 3D
clustered-based coordination material 3. PXRD patterns have been characterized
confirming coordination polymers 1-3 are pure samples. Photo-luminescent
investigations demonstrated that 1-3 can be utilized as bi-functional sensors for Fe3+
and NZF antibiotics with high efficiency Ksv values (For Fe3+: 7.28×104 M-1 for 1;
3.38×104 M-1 for 2 and 3.29×104 M-1 for 3 and for NZF antibiotics: 4.47×103 M-1
for 1; 4×103 M-1 for 2 and 5.6×103 M-1 for 3). The result also represents these
asymmetrical π-electron-rich aromatic polycarboxylate linkers have great applications
in the preparation of these unique cluster-based coordination polymers with beautiful
structural motifs and ideal photo-luminescent sensing properties. On the basis of this
work, further design, synthesis and functional application characterization of
coordination materials based on these rigid asymmetrical π-electron-rich ligands are
also under way in our laboratory.
Supporting Information Available: Listings of Crystallographic data for 1-3 in CIF
format, Selected Bond Lengths [Å] and Angles [º] of 1-3, PXRD patterns of 1-3, TGA
curve of 1-3, Photo-luminescent spectra of H4L and coordination polymers 1-3
dispersed in water solutions..
Acknowledgments. This work was supported financially by the Foundation of
Development Program of Future Expert in Tianjin Normal University (WLQR201801)
，the Open Project of Key Lab Adv Energy Mat Chem (Nankai Univ), 111 project
(B12015), Natural Science Foundation of Tianjin (Grant no. 18JCYBJC89700),
Young Scientist Fund (Grant no. 21301128) and the Program for Innovative Research
Team in University of Tianjin (TD13-5074).
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