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Structural diversity and fluorescent sensing of four novel complexes based on rigid terphenyl-3,3″,5,5″-tetracarboxylic acid
Accepted Manuscript Structural diversity and fluorescent sensing of four novel complexes based on rigid terphenyl-3,3″,5,5″-tetracarboxylic acid Jinxia Liang, Qiannan Zhao, Lingling Gao, Jie Zhang, Xiaoyan Niu, Tuoping Hu PII:
S0022-4596(19)30157-4
DOI:
https://doi.org/10.1016/j.jssc.2019.03.047
Reference:
YJSSC 20696
To appear in:
Journal of Solid State Chemistry
Received Date: 14 February 2019 Revised Date:
24 March 2019
Accepted Date: 24 March 2019
Please cite this article as: J. Liang, Q. Zhao, L. Gao, J. Zhang, X. Niu, T. Hu, Structural diversity and fluorescent sensing of four novel complexes based on rigid terphenyl-3,3″,5,5″-tetracarboxylic acid, Journal of Solid State Chemistry (2019), doi: https://doi.org/10.1016/j.jssc.2019.03.047. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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ACCEPTED MANUSCRIPT Journal of Solid State Chemistry journal homepage: www.elsevier.com/locate/jssc
Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Jinxia Lianga, Qiannan Zhaoa, Lingling Gaoa, Jie Zhanga, Xiaoyan Niua, and Tuoping Hua*
Department of Chemistry, College of Science, North University of China, Taiyuan 030051, China.
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Keywords: Complex; Fluorescent properties; Fe(III) ion; Nitrobenzene derivatives
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ACCEPTED MANUSCRIPT ABSTRACT Based on H4TPTC and 1,2-bimb/1,3-bimb ligands, four novel complexes, namely, {[Cu(TPTC)(1,2bimb)2]·4.5(H2O)}n (1), [Cu(TPTC)0.5(1,3-bimb)]n (2), {[Eu2(TPTC)1.5(H2O)4]·4.5(H2O)·2(1,4–DOX)}n (3) and {[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4–DOX)}n (4) have been constructed under solvothermal conditions [H4TPTC = terphenyl-3,3”,5,5”-tetracarboxylic acid, 1,3-bimb = 1,3-bis (imidazol-1-ylmethyl) benzene, 1,2-bimb = 1,2-bis (imidazol-1-ylmethyl) benzene]. Complexes 1 and 2 are 4-connected 2D networks with the topological types of sql (1)
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and kgm (2). Complex 3 exhibits a 4, 4, 12-connected network with the point symbol of {432.634}{44.62}{46}2. Complex 4 presents a 3D supramolecular network through hydrogen bonds. The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity for Cr2O72- and Fe3+ ions in aqueous solutions, and 3 can
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selectively detect NDVs. Furthermore, possible mechanism for luminescence quenching was also investigated.
Contents lists available at SciVerse ScienceDirect
ACCEPTED MANUSCRIPT Journal of Solid State Chemistry journal homepage: www.elsevier.com/locate/jssc
Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Jinxia Lianga, Qiannan Zhaoa, Lingling Gaoa, Jie Zhanga, Xiaoyan Niua, and Tuoping Hua*
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Department of Chemistry, College of Science, North University of China, Taiyuan 030051, China. ABSTRACT: Based on H4TPTC and 1,2-bimb/1,3-bimb ligands, four novel complexes, namely, {[Cu(TPTC)(1,2-bimb)2]·4.5(H2O)}n (1), [Cu(TPTC)0.5(1,3-bimb)]n (2), {[Eu2(TPTC)1.5(H2O)4]·4.5(H2O)·2(1,4–DOX)}n (3) and {[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4–DOX)}n (4) have been constructed under solvothermal conditions [H4TPTC = terphenyl-3,3”,5,5”-tetracarboxylic acid, 1,3-bimb = 1,3-bis (imidazol-1-ylmethyl) benzene, 1,2-bimb = 1,2-bis (imidazol-1-ylmethyl) benzene]. Complexes 1 and 2 are 4-connected 2D networks with the topological types of sql (1) and kgm (2). Complex 3 exhibits a 4, 4, 12-connected network with the point symbol of {432.634}{44.62}{46}2. Complex 4 presents a 3D supramolecular network through hydrogen bonds. The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity for Cr2O72- and Fe3+ ions in aqueous solutions, and 3 can selectively detect NDVs. Furthermore, possible mechanism for luminescence quenching was also investigated.
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ARTICLEINFO Keywords: Complex Fluorescent properties Fe(III) ion Nitrobenzene derivatives
1. Introduction
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Coordination polymers (CPs), as a kind of inorganic-organic hybrid material,[1-6] have potential applications in microelectronics, gas storage,[7-9] fluorescence recognition,[10-13] chemical separation, magnetic material[14] and nonlinear optics due to their attractive structure and novel topology. In 2009,[15] a fluorescent Zn-MOF was firstly synthesized and reported, and used as a fluorescent probe for sensing nitroaromatics. In recent years, it has become a research hotspot of fluorescent materials that the syntheses of fluorescent CPs and the research on the sensing properties of CPs for organic small molecules or ions. [1617] In the construction of fluorescent CPs, the rational choice of the linkers and the center metal ions is crucial, because the charge transfer between them will affect the fluorescence properties of CPs. Many heavy metal ions (Fe3+, Cr6+) play an indispensable role in industrial development and human survival. For example, Fe3+ ion plays an important role in life metabolism and oxygen absorption, while Cr6+ ion is widely used in industry. Due to the industrial wastewater discharge and inadvertently discarded rubbish, excessive heavy metal ions in aqueous solutions can cause long-term damage to the environment and human body. [1821] Furthermore, aromatic nitro derivatives are important chemical raw materials, but their improper storage and use will pose a great threat to people's health. [22, 23] So it is very urgent to seek a rapid detection method of heavy metal ions and organic small molecules. Compared with the conventional methods, fluorescent probe is an effective method on the recognition metal ions and organic small molecules, due to a fast response speed, a low detection limit, energy saving, low cost and simple operation. [24] Inspired by the above situation, terphenyl-3,3",5,5"-
*Corresponding author. E-mail: [email protected](T.P. Hu). Received Xth XXXXXXXXX 2019; Received in revised form Xth XXXXXXXXX 2019; Accepted Xth XXXXXXXXX 2019; Available online Xth XXXXXXXXX 2019
tetracarboxylic acid (H4TPTC) was selected based on the following reasons: (1) the rigid framework of H4TPTC ligand helps to construct stable CPs. (2) its carboxyl groups can adopt diverse coordination modes, which provide the possibility to construct the CPs with the novel structures and excellent properties. (3) its conjugated aromatic rings facilitate the electron transport, which will affect fluorescence properties of CPs to some extent. In addition, H4TPTC ligand has already been used to synthesize many CPs, which have been widely used in the field of magnetic and fluorescent materials.[25-27] Meanwhile, 1,3-bimb and 1,2-bimb can also be used as auxiliary ligands to control the final structures and properties of CPs due to their advantages of small steric hindrance and linear structure. [28] In this work four novel CPs have been constructed under solvothermal methods. Furthermore, fluorescent properties of 1 and 3 were investigated in detail. 2. Experimental
2.1 Reagents and Methods All solvents and reagents are commercially available and used directly. X-ray crystallography, physical characterizations and fluorescent measurements can be seen in Supporting Information.
2.2. Syntheses of complexes 1-4 Synthesis of {[Cu 2(TPTC)(1,2-bimb)2]·4.5(H2O)}n (1): H4TPTC (2.1 mg, 0.005 mmol), 1,2-bimb (2.4 mg, 0.010 mmol) and CuCl2·6H2O (3.8 mg, 0.015 mmol) were dissolved in 4 mL H2O/CH3CN mixed solution (v:v = 1:1). The mixture was placed in a reaction vessel and heated to 130 °C for 3 days. After gradually dropping to ambient temperature, blue needle crystals were obtained. (yield: 35%, based on Cu). Elemental analysis (%): calcd for C50H47Cu 2N8O12.5: C, 55.20; H, 4.32; N, 10.30. Found: C, 54.95; H, 4.24; N, 10.68. IR (KBr pellet, cm-1): 3442 (vs), 1636 (vs), 1560 (vs), 1512 (s),
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ACCEPTED MANUSCRIPT Synthesis of [Cu(TPTC)0.5(1,3-bimb)]n (2): H4TPTC (0.006 mmol, 2.5 mg), 1,3-bimb (0.006 mmol, 1.5 mg) and CuCl2·6H2O (0.018 mmol, 4.4 mg) were placed in 1mL H2O/DMF mixed solution (v/v = 1/1), which was transferred to a hard glass tube, heated to 130 °C for three days. After gradually dropping to room temperature, blue block crystals were gained with the yield of 43% (based on Cu). Elemental analysis (%): calcd for C25H19CuN4O4: C, 59.64; H, 3.77; N, 11.13. Found: C, 59.54; H, 3.75; N, 11.18. IR (KBr pellet, cm-1): 3488 (vs), 1613 (vs), 1564 (vs), 1514 (s), 1402 (s), 1354 (m), 740 (s), 735 (s), 693 (m), 688 (m). Synthesis DOX)}n (3):
of
{[Eu 2(TPTC)1.5(H2O)4]·4.5(H2O)·2(1,4–
from Fig. 1a, there are one TPTC4- linker, two 1,2-bimb linkers, and two Cu(II) ions in the asymmetric unit of 1. Cu1 and Cu2ii ions have the same coordination environment. Cu1 ions are linked by three O-atoms (O1, O3i, O6ii) from three different TPTC4- linkers, two N-atoms (N5, N4ii) from two different 1,2bimb linkers, forming a trigonal bipyramid geometry. The Cu– O/N separations are from 1.964(3) to 2.287(4) Å, and the O–Cu– N/O angles are in the range of 85.56(13) ° to 174.98(18) °. The adjacent Cu1 and Cu2ii ions are connected with two carboxyl groups to form binuclear [Cu2(COO)4] SBUs (Fig. 1b), which are linked by 1,2-bimb and TPTC4- linkers with µ6-η1:η1:η1:η1:η1:η1 bonding mode (Mode (I), Scheme 1) to construct a 2D structure (Fig. 1c). By topology, when both TPTC4- ligands and [Cu2(COO)4] SBUs can be served as 4-connected nodes, the topology type of 1 is sql (Fig. 1d).
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1455 (s), 1354 (vs), 986 (m), 977 (m), 861 (s), 780 (s), 765 (s), 682 (m), 638 (m).
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The mixture of H4TPTC (0.010 mmol, 4.2 mg), Eu(NO3)3·6H2O (0.030 mmol, 13.4 mg), diluted ammonia (3 drops, 0.25 mol/L), 4 mL H2O and 4 mL 1,4-dioxane were added to a reaction vessel, heated to 130 °C for three days. After being cooled to ambient temperature for one day, colorless flaky crystals were gained. (yield: 36%, based on Eu). Elemental analysis (%): calcd for C41H48Eu2O24.5: C, 39.78; H, 3.88. Found: C, 39.72; H, 3.92. IR (KBr pellet, cm-1): 3419 (vs), 1623 (vs), 1451 (vs), 1564 (s), 1408 (vs), 986 (m), 977 (m), 870 (s), 782 (s), 773 (s), 685 (m), 653 (m). Synthesis of {[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4-DOX)}n (4):
Fig. 1. (a) The bonding environment of the Cu(II) ions in complex 1 (symmetry codes: (i) -1+x, y, z; (ii) -0.5+x, 0.5-y, 0.5+z; (iii) 0.5+x, 0.5-y, -0.5+z; (iv) 1+x, y, z.). (b) The binuclear [Cu2(COO)4] SBUs in 1. (c) The 2D structure of 1. (d) The topology of 1.
3.1.2 Structural description of [Cu(TPTC)0.5(1,3-bimb)]n (2)
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The synthetic procedures are the same as that of 3 except that Ce(NO3)3·6H2O (0.030 mmol, 13.0 mg) is substituted for Eu(NO3)3. Colorless flaky crystals were collected with the yield of 35% (based on Ce). Elemental analysis (%): calcd for C48H48Ce2O27: C, 43.07; H, 3.58. Found: C, 42.94; H, 3.55. IR (KBr pellet, cm-1): 3450 (vs), 1623 (vs), 1451 (vs), 1405 (vs), 976 (m), 967 (m), 869 (s), 762 (s), 753 (s), 695 (m), 643 (m).
Scheme 1. The bonding patterns of TPTC4- in CPs 1-4.
3. Results and Discussion 3.1 Descriptions of crystal structures 3.1.1 Structural description bimb)2]·4.5(H2O)}n (1)
of
{[Cu2(TPTC)(1,2-
According to X-ray diffraction analysis, complex 1 belongs to the monoclinic system and P21/n space group. As can be seen
Fig. 2. (a) The bonding situation of the Cu(II) ions. (b) The 2D structure of 2. (c) The topological structure of 2.
ACCEPTED MANUSCRIPT structure of 3 is simplified as a (4, 4, 12)-c network with the point symbol of {432.634}{44.62}{46}2 (Fig. 3d).
3.1.4
Structural
description
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{[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4-DOX)}n (4)
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Analysis of crystal data showed that complex 4 belongs to the monoclinic system with C2/c space group. There are one Ce(III) ion, one TPTC4- linker, four coordination water molecules, half of 1,4-dioxane and half of the lattice water molecules in the repeating unit. As can be seen from Fig. 4a, Ce1 is coordinated with five O-atoms (O1i, O2i, O4, O7ii, O6iii) from four TPTC4ligands and four O-atoms (O1W, O2W, O3W, O4W) from four coordination water molecules. The Ce1–O separations vary from 2.517(2) Å to 2.582(2) Å, and the O–Ce1–O bond angles vary from 51.10(8) to 146.14(9) °. Ce(III) ions were linked by TPTC4ligands adopting the µ4-η2:η1:η1:η1 bonding mode (V) (Scheme 1) to form a 2D structure (Fig. 4b), which is further packed into 3D supramolecular structures (Fig. 4d) by H-bonding interaction involving the coordinated water molecules, lattice 1,4-dioxane molecules and uncoordinated oxygen atoms from ligands. The details of hydrogen bonds are listed in Table S3. Topologically, the 2D structure can be simplified as a 4-c network with the point symbol of {44.62} (Fig. 4c).
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Analysis of crystal data showed that complex 2 crystalizes in monoclinic system and C2/c space group, and the repeating unit consists of half of TPTC4− linkers, one 1,3-bimb linker and one Cu(II) ion. Cu1 ion is surrounded by two O-atoms (O1, O2) from two TPTC4− linkers and two N-atoms (N1, N3) from two different 1,3-bimb linkers, exhibiting a quadrilateral geometry (Fig. 2a). The Cu–N/O distances vary from 1.974(3) to 1.990(3) Å, and the O–Cu–O/N angles vary from 88.50(9) ° to 174.46(12) °, respectively. In 2, Cu(II) ions are connected with TPTC4- and 1,3-bimb ligands to form a 2D structure (Fig. 2b), in which the TPTC4- ligand adopts a bonding mode of µ4η1:η1:η1:η1 (Mode (II), Scheme 1). Topologically, the 2D structure can be simplified as a 4-c kgm type topology with the point symbol of {32.62.72} (Fig. 2c).
3.1.3
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Fig. 3. (a) The bonding situation of the Eu(III) ions (symmetry code: (vi) 1-x, 1-y, -z; (vii) 1-x, 1-y, -1-z; (viii) 2-x, 1-y, 1-z; (ix) 1-x, -y, 2-z; (x) x, 1+y, 1+z; (xi) -1+x, y, z; (xii) x, y, -1+z.). (b) The [Eu4(COO)12] cluster in 3. (c) The 3D network of 3. (d) The topology of 3.
description
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Analysis of crystal data indicated that complex 3 is attributed to the triclinic system with P-1 space group. The asymmetric unit of 3 consists of two Eu(III) ions, one and half of TPTC4− linkers, four coordinated water molecules, two lattice 1,4-dioxane molecules and four and half lattice water molecules. As can be seen from Fig. 3a, Eu1vi is coordinated with seven O-atoms (O4vi, O12vi, O3, O11vi, O10xiii, O4vi, O2viii) from five TPTC4− linkers and two O-atoms (O2Wvi, O3Wvi) from two lattice water molecules. Eu2xiii is surrounded by six O-atoms (O1viii, O9xiii, O6xv, O7xiv, O8xiv and O5xv) from the four TPTC4− ligands and two O-atoms (O4Wxiii, O5Wxiii) from two lattice water molecules. The Eu–O distances vary from 2.278(4) Å to 3.056(5) Å. The O– Eu–O angles vary from 52.18(14) ° to 153.32(16) °. In 3, four Eu(III) ions are linked by twelve carboxyl groups to form [Eu4(COO)12] SBUs (Fig. 3b), which were expanded by TPTC4ligands adopting the coordination modes of µ4-η2:η2:η2:η2 (III) and µ7-η1:η1:η2:η1:η1:η2:η1 (IV)(Scheme 1) to construct a complicated 3D structure (Fig. 3c). Topologically, when the tetranuclear [Eu4(COO)12] SBUs and TPTC4- ligands are taken as 12-connected nodes and 4-connectd nodes respectively, the
Fig. 4. (a) The coordination situation of the Ce(III) ions (symmetry code: (i) x, -y, 0.5+z; (ii) 1.5-x, 0.5+y, 1.5-z; (iii) x, -y, -0.5+z; (iv) 0.5+x, -0.5+y, z; (v) -0.5+x, 0.5+y, z; (vi) x, -1+y, z ). (b)The 2D network of 4 viewed on b axis perspective. (c) The topological structure of 4. (d) The 3D network of 4 formed by hydrogen-bonding.
3.2.2 Powder X-ray diffraction analyses (PXRD) and thermal analyses (TG). The PXRD diagrams of complexes 1-4 were shown in Fig. S1, and the pivotal peak positions of the measured PXRD patterns are almost the same as those of the simulated ones, demonstrating that the title complexes have good phase purity. Thermogravimetric measurements were carried out to check the thermal stability of 1-4 (Fig. S2). For 1, the weight loss of 7.52% (calcd: 7.45%) is assigned to the loss of four and a half lattice water molecules below 130 °C. The weight loss of 77.08% (calcd: 77.47%) is attributed to the loss of two 1,2-bimb ligands and a TPTC4- ligand between 290 and 500 °C. After that, its framework completely decomposes and the residue is CuO. As for 2, the framework begins to decompose above 260 °C and completely collapse at 650 °C. The residue is CuO of 16.58% (calcd:
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3.3 Fluorescent Properties
To check the recognition sensitivity of 1 for metal ions, a series of M(NO3)n solutions (0.01mol·L-1, M = Ag+, K+, Na+, Co2+, Ba2+, Pb2+, Ni2+, Cd2+, Cu2+, Mn2+, Al3+ and Fe3+) were selected as the analytes. The finely samples of 1 (2 mg) were ground and dissolved in 2 mL M@H2O suspension solution with the ultrasonic treatment for 30 min. As shown in Fig. 6, fluorescent intensity of Fe3+ for 1 was almost quenched by comparing with other metal ions, which indicated that 1 is sensitive to Fe3+ ions. In order to further explore the effect of the concentration gradient of Fe3+ on fluorescent intensity of 1, as exhibited in Fig. 7, the results showed that the fluorescent intensity of 1 gradually decreased to almost zero with the increasing Fe3+ concentration to be 0.125 mM. Nonlinear fitting of I0/I and the Fe3+ concentrations can be expressed by an exponential equation, where I0 and I are the fluorescent intensity of 1@H2O and 1@Mn+, respectively. It can be found that there is a linear Stern-Volmer equation (SV): (I0/I) = 1 + Ksv [M] at low concentration (Ksv and [M] represent the quenching constant and the concentration of metal ions (mM), respectively). The Ksv value was found to be 3.4 × 104 M−1, which is higher than that of the previously reported Eu-based CPs, for instance, MIL-53COOH (Al) (5.12 × 103 M−1), [Ln(cptpy)3]n (4.1 × 103 M−1) and Eu-MOF-LIC-1 (2.87 × 104 M−1) [37-39]. These results showed that complex 1 has good fluorescence sensitivity for Fe3+.The detection limit (2.5 × 10-4 M) was calculated by 3σ/Ksv (σ is the standard deviations for three cycles fluorescence tests of blank solutions at room temperature. The values of σ and exponential equation are in Table S4 and S5).
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The emission spectra of complexes 1 and 3, H4TPTC and 1,2bimb ligands were tested at room temperature in the solid state (Fig. 5). The maximum peaks of the H4TPTC and 1,2-bimb ligands are at 408 nm and 437 nm (λex=280 nm) respectively, which are derived from the electronic transitions of π-π* or π*n.[28-30]
617 nm is consistent with the previously reported Eu-based MOF.[1, 35, 36]
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15.91%). For 3, the weight loss of 12.32% (calcd: 12.37%) in the range of 60–150 °C corresponds to the loss of four and a half lattice water molecules and four coordination water molecules. The weight loss of 14.18% (calcd: 14.23%) is due to the loss of two 1,4-dioxane from 250 °C to 300 °C. The framework is stable until the temperature is up to 390 °C. As for 4, the weight loss of 19.25% (calcd: 19.28%) under 274 °C is assigned to the loss of four coordination water molecules, half of lattice 1,4-dioxane molecules and half of lattice water molecules. The framework begins to collapse beyond 450 °C.
Fig. 5. Solid fluorescence spectra of complexes 1 and 3, H4TPTC and 1,2-bimb ligands.
Compared to H4TPTC ligand, the maximum emission peak of 1 at 328 nm is blue-shifted by 80 nm, which may be that the bonding modes between metal ions and ligands increase effectively the rigidity of complexes and reduce the loss of nonradiative energy.[32-34] As for 3, the characteristic emission peaks are at 536 nm, 590 nm, 617 nm respectively, which are attributed to electronic transitions (5D0-7FJ, J=0-4) of Eu3+ ion, respectively (Fig. 5). Especially, the strongest characteristic emission peak at
Fig. 6. The fluorescence intensity of complex 1 which were dispersed in M(NO3)n solutions.
Furthermore, inspired by the experiments of metal ions, the recognition sensitivity of anions was also tested. The experimental procedures were similar to those of metal ions except for replacing M(NO3)n with KnX (0.01 mol·L-1, X = Cl-, Br-, I-, SCN-, H2PO4-, HCO3-, CO32-, NO3-, SO42-, C2O42- and Cr2O72-). As exhibited in Fig. S3, fluorescence intensity of 1 was almost completely quenched by Cr2O72- ion compared with other anions. As the calculation method of metal ions, the value of Ksv and the detection limit were calculated to be 4.9×104 M−1 and 1.8 × 10-4 M, respectively, which is larger than the previously reported. [40] The PXRD patterns of samples after fluorescence tests are almost the same as the simulated ones (Fig. S4), which indicate that complex 1 is stable and don’t have coordination with ions. The possible reason of fluorescence quenching is that the
ACCEPTED MANUSCRIPT addition of ions affects the antenna effect of the ligand in complex 1, which can be verified by the UV-visible absorption study.[41] The excitation spectrum of 1 shows an obvious overlap with the UV-visible absorption spectra of ions (Fig. S5), which indicated that there are energy competitive absorption. Furthermore, the weak interaction between ions and uncoordinated carboxyl oxygen atoms is also one of the causes of fluorescence quenching.
Ksv value and the detection limit are found to be 1.0 × 104 M−1 and 6.2 × 10-4 M, respectively. The possible quenching mechanism of NDVs for 3 is attributed to the energy transfer between the electron-rich complex 3 and the electron-deficient NDVs. [42] In addition, there are energy competitive absorption between complex and the analyte, which can be verified by the UV-visible absorption studies. The results show that there are an obvious overlap between the UV-visible absorption spectra of NDVs and the excitation spectrum of 1 (Fig. S8).
Conclusions
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In summary, four novel complexes have been synthesized based on rigid terphenyl-3,3",5,5"-tetracarboxylic acid under solvothermal methods. The experimental results showed complex 1 has good fluorescence sensitivity for Fe3+ and Cr2O72- ions in aqueous solutions, which shows it has the potential as a dualfunctional detecting sensor for Fe3+ and Cr2O72- ions with low detection limits. Complex 3 has obvious detection sensitivity for NDVs. Moreover, the detecting mechanisms are also discussed. These results provide theoretical and experimental guidance for the further synthesis of fluorescence recognition materials with excellent properties.
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Fig. 7. Fluorescence spectra of complex 1 in aqueous solutions with the concentration of Fe3+ increase. Inset: nonlinear fitting of fluorescence quenching and linear fitting at low concentration.
The authors gratefully acknowledge the National Natural Science Foundation of China (No: 21676258), the international Scientific and Technological Cooperation Projects of Shanxi Province (No: 201803D421080) and the support of innovative research team of inorganic-organic hybrid functional materials in North University of China.
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Appendix A. Supplementary data
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Fig. 8. Fluorescence spectra of complex 3 in DMF as the concentration of NT increase. Inset: linear fitting of fluorescence quenching at low concentration.
Interestingly, as it is exhibited in Fig. S6 that complex 3 has obvious recognition sensitivity for nitrobenzene. Thus, the sensing experiments of 3 for other nitrobenzene derivatives (NDVs) (nitrobenzene (NB), p-nitroaniline (NA), p-nitrotoluene (NT), and p-nitrophenol (NP)) were also carried out. The results showed that the quenching efficiency of NDVs for 3 is NT>NA>NB>NP, and the quenching rate reached 98% when the concentration of NT was 1.5 mM (Fig. S7 and Fig. 8). The quenching constant can be expressed with the SV equation: (I0/I) = 1 + Ksv [M], where I0 and I are fluorescence intensities of 3 in blank DMF solution and upon adding NDVs, respectively. At low concentrations, the SV plot for NT is nearly linear, and the
The Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on quoting the depository numbers CCDC 1882252, 1882253, 1882521, 1882254 (Fax: +44-1223-33-033; E-Mail: [email protected], http://www.ccdc. cam. ac.uk).
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Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Highlights:
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(1) Four novel complexes have been synthesized based on rigid terphenyl-3,3",5,5"-tetracarboxylic acid by solvothermal methods.
(2) The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity
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for Fe3+ and Cr2O72- ions in aqueous solutions, and 3 can selectively detect NDVs.
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Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Jinxia Lianga, Qiannan Zhaoa, Lingling Gaoa, Jie Zhanga, Xiaoyan Niua, and Tuoping Hua*
Synopsis:
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Four novel complexes have been synthesized based on rigid terphenyl-3,3",5,5"-tetracarboxylic acid by solvothermal methods. The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity for Fe3+ and Cr2O72- ions in aqueous solutions, and 3 can selectively detect NDVs.
Journal Name,1 [year], [vol], 00–00
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2 ournal Name, [year], [vol], 00–00This journal is © The Royal Society of Chemistry [year]
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S0022-4596(19)30157-4
DOI:
https://doi.org/10.1016/j.jssc.2019.03.047
Reference:
YJSSC 20696
To appear in:
Journal of Solid State Chemistry
Received Date: 14 February 2019 Revised Date:
24 March 2019
Accepted Date: 24 March 2019
Please cite this article as: J. Liang, Q. Zhao, L. Gao, J. Zhang, X. Niu, T. Hu, Structural diversity and fluorescent sensing of four novel complexes based on rigid terphenyl-3,3″,5,5″-tetracarboxylic acid, Journal of Solid State Chemistry (2019), doi: https://doi.org/10.1016/j.jssc.2019.03.047. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Contents lists available at SciVerse ScienceDirect
ACCEPTED MANUSCRIPT Journal of Solid State Chemistry journal homepage: www.elsevier.com/locate/jssc
Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Jinxia Lianga, Qiannan Zhaoa, Lingling Gaoa, Jie Zhanga, Xiaoyan Niua, and Tuoping Hua*
Department of Chemistry, College of Science, North University of China, Taiyuan 030051, China.
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Keywords: Complex; Fluorescent properties; Fe(III) ion; Nitrobenzene derivatives
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ACCEPTED MANUSCRIPT ABSTRACT Based on H4TPTC and 1,2-bimb/1,3-bimb ligands, four novel complexes, namely, {[Cu(TPTC)(1,2bimb)2]·4.5(H2O)}n (1), [Cu(TPTC)0.5(1,3-bimb)]n (2), {[Eu2(TPTC)1.5(H2O)4]·4.5(H2O)·2(1,4–DOX)}n (3) and {[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4–DOX)}n (4) have been constructed under solvothermal conditions [H4TPTC = terphenyl-3,3”,5,5”-tetracarboxylic acid, 1,3-bimb = 1,3-bis (imidazol-1-ylmethyl) benzene, 1,2-bimb = 1,2-bis (imidazol-1-ylmethyl) benzene]. Complexes 1 and 2 are 4-connected 2D networks with the topological types of sql (1)
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and kgm (2). Complex 3 exhibits a 4, 4, 12-connected network with the point symbol of {432.634}{44.62}{46}2. Complex 4 presents a 3D supramolecular network through hydrogen bonds. The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity for Cr2O72- and Fe3+ ions in aqueous solutions, and 3 can
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selectively detect NDVs. Furthermore, possible mechanism for luminescence quenching was also investigated.
Contents lists available at SciVerse ScienceDirect
ACCEPTED MANUSCRIPT Journal of Solid State Chemistry journal homepage: www.elsevier.com/locate/jssc
Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Jinxia Lianga, Qiannan Zhaoa, Lingling Gaoa, Jie Zhanga, Xiaoyan Niua, and Tuoping Hua*
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Department of Chemistry, College of Science, North University of China, Taiyuan 030051, China. ABSTRACT: Based on H4TPTC and 1,2-bimb/1,3-bimb ligands, four novel complexes, namely, {[Cu(TPTC)(1,2-bimb)2]·4.5(H2O)}n (1), [Cu(TPTC)0.5(1,3-bimb)]n (2), {[Eu2(TPTC)1.5(H2O)4]·4.5(H2O)·2(1,4–DOX)}n (3) and {[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4–DOX)}n (4) have been constructed under solvothermal conditions [H4TPTC = terphenyl-3,3”,5,5”-tetracarboxylic acid, 1,3-bimb = 1,3-bis (imidazol-1-ylmethyl) benzene, 1,2-bimb = 1,2-bis (imidazol-1-ylmethyl) benzene]. Complexes 1 and 2 are 4-connected 2D networks with the topological types of sql (1) and kgm (2). Complex 3 exhibits a 4, 4, 12-connected network with the point symbol of {432.634}{44.62}{46}2. Complex 4 presents a 3D supramolecular network through hydrogen bonds. The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity for Cr2O72- and Fe3+ ions in aqueous solutions, and 3 can selectively detect NDVs. Furthermore, possible mechanism for luminescence quenching was also investigated.
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ARTICLEINFO Keywords: Complex Fluorescent properties Fe(III) ion Nitrobenzene derivatives
1. Introduction
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Coordination polymers (CPs), as a kind of inorganic-organic hybrid material,[1-6] have potential applications in microelectronics, gas storage,[7-9] fluorescence recognition,[10-13] chemical separation, magnetic material[14] and nonlinear optics due to their attractive structure and novel topology. In 2009,[15] a fluorescent Zn-MOF was firstly synthesized and reported, and used as a fluorescent probe for sensing nitroaromatics. In recent years, it has become a research hotspot of fluorescent materials that the syntheses of fluorescent CPs and the research on the sensing properties of CPs for organic small molecules or ions. [1617] In the construction of fluorescent CPs, the rational choice of the linkers and the center metal ions is crucial, because the charge transfer between them will affect the fluorescence properties of CPs. Many heavy metal ions (Fe3+, Cr6+) play an indispensable role in industrial development and human survival. For example, Fe3+ ion plays an important role in life metabolism and oxygen absorption, while Cr6+ ion is widely used in industry. Due to the industrial wastewater discharge and inadvertently discarded rubbish, excessive heavy metal ions in aqueous solutions can cause long-term damage to the environment and human body. [1821] Furthermore, aromatic nitro derivatives are important chemical raw materials, but their improper storage and use will pose a great threat to people's health. [22, 23] So it is very urgent to seek a rapid detection method of heavy metal ions and organic small molecules. Compared with the conventional methods, fluorescent probe is an effective method on the recognition metal ions and organic small molecules, due to a fast response speed, a low detection limit, energy saving, low cost and simple operation. [24] Inspired by the above situation, terphenyl-3,3",5,5"-
*Corresponding author. E-mail: [email protected](T.P. Hu). Received Xth XXXXXXXXX 2019; Received in revised form Xth XXXXXXXXX 2019; Accepted Xth XXXXXXXXX 2019; Available online Xth XXXXXXXXX 2019
tetracarboxylic acid (H4TPTC) was selected based on the following reasons: (1) the rigid framework of H4TPTC ligand helps to construct stable CPs. (2) its carboxyl groups can adopt diverse coordination modes, which provide the possibility to construct the CPs with the novel structures and excellent properties. (3) its conjugated aromatic rings facilitate the electron transport, which will affect fluorescence properties of CPs to some extent. In addition, H4TPTC ligand has already been used to synthesize many CPs, which have been widely used in the field of magnetic and fluorescent materials.[25-27] Meanwhile, 1,3-bimb and 1,2-bimb can also be used as auxiliary ligands to control the final structures and properties of CPs due to their advantages of small steric hindrance and linear structure. [28] In this work four novel CPs have been constructed under solvothermal methods. Furthermore, fluorescent properties of 1 and 3 were investigated in detail. 2. Experimental
2.1 Reagents and Methods All solvents and reagents are commercially available and used directly. X-ray crystallography, physical characterizations and fluorescent measurements can be seen in Supporting Information.
2.2. Syntheses of complexes 1-4 Synthesis of {[Cu 2(TPTC)(1,2-bimb)2]·4.5(H2O)}n (1): H4TPTC (2.1 mg, 0.005 mmol), 1,2-bimb (2.4 mg, 0.010 mmol) and CuCl2·6H2O (3.8 mg, 0.015 mmol) were dissolved in 4 mL H2O/CH3CN mixed solution (v:v = 1:1). The mixture was placed in a reaction vessel and heated to 130 °C for 3 days. After gradually dropping to ambient temperature, blue needle crystals were obtained. (yield: 35%, based on Cu). Elemental analysis (%): calcd for C50H47Cu 2N8O12.5: C, 55.20; H, 4.32; N, 10.30. Found: C, 54.95; H, 4.24; N, 10.68. IR (KBr pellet, cm-1): 3442 (vs), 1636 (vs), 1560 (vs), 1512 (s),
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ACCEPTED MANUSCRIPT Synthesis of [Cu(TPTC)0.5(1,3-bimb)]n (2): H4TPTC (0.006 mmol, 2.5 mg), 1,3-bimb (0.006 mmol, 1.5 mg) and CuCl2·6H2O (0.018 mmol, 4.4 mg) were placed in 1mL H2O/DMF mixed solution (v/v = 1/1), which was transferred to a hard glass tube, heated to 130 °C for three days. After gradually dropping to room temperature, blue block crystals were gained with the yield of 43% (based on Cu). Elemental analysis (%): calcd for C25H19CuN4O4: C, 59.64; H, 3.77; N, 11.13. Found: C, 59.54; H, 3.75; N, 11.18. IR (KBr pellet, cm-1): 3488 (vs), 1613 (vs), 1564 (vs), 1514 (s), 1402 (s), 1354 (m), 740 (s), 735 (s), 693 (m), 688 (m). Synthesis DOX)}n (3):
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from Fig. 1a, there are one TPTC4- linker, two 1,2-bimb linkers, and two Cu(II) ions in the asymmetric unit of 1. Cu1 and Cu2ii ions have the same coordination environment. Cu1 ions are linked by three O-atoms (O1, O3i, O6ii) from three different TPTC4- linkers, two N-atoms (N5, N4ii) from two different 1,2bimb linkers, forming a trigonal bipyramid geometry. The Cu– O/N separations are from 1.964(3) to 2.287(4) Å, and the O–Cu– N/O angles are in the range of 85.56(13) ° to 174.98(18) °. The adjacent Cu1 and Cu2ii ions are connected with two carboxyl groups to form binuclear [Cu2(COO)4] SBUs (Fig. 1b), which are linked by 1,2-bimb and TPTC4- linkers with µ6-η1:η1:η1:η1:η1:η1 bonding mode (Mode (I), Scheme 1) to construct a 2D structure (Fig. 1c). By topology, when both TPTC4- ligands and [Cu2(COO)4] SBUs can be served as 4-connected nodes, the topology type of 1 is sql (Fig. 1d).
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1455 (s), 1354 (vs), 986 (m), 977 (m), 861 (s), 780 (s), 765 (s), 682 (m), 638 (m).
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The mixture of H4TPTC (0.010 mmol, 4.2 mg), Eu(NO3)3·6H2O (0.030 mmol, 13.4 mg), diluted ammonia (3 drops, 0.25 mol/L), 4 mL H2O and 4 mL 1,4-dioxane were added to a reaction vessel, heated to 130 °C for three days. After being cooled to ambient temperature for one day, colorless flaky crystals were gained. (yield: 36%, based on Eu). Elemental analysis (%): calcd for C41H48Eu2O24.5: C, 39.78; H, 3.88. Found: C, 39.72; H, 3.92. IR (KBr pellet, cm-1): 3419 (vs), 1623 (vs), 1451 (vs), 1564 (s), 1408 (vs), 986 (m), 977 (m), 870 (s), 782 (s), 773 (s), 685 (m), 653 (m). Synthesis of {[Ce(TPTC)(H2O)4]·0.5(H2O)·0.5(1,4-DOX)}n (4):
Fig. 1. (a) The bonding environment of the Cu(II) ions in complex 1 (symmetry codes: (i) -1+x, y, z; (ii) -0.5+x, 0.5-y, 0.5+z; (iii) 0.5+x, 0.5-y, -0.5+z; (iv) 1+x, y, z.). (b) The binuclear [Cu2(COO)4] SBUs in 1. (c) The 2D structure of 1. (d) The topology of 1.
3.1.2 Structural description of [Cu(TPTC)0.5(1,3-bimb)]n (2)
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The synthetic procedures are the same as that of 3 except that Ce(NO3)3·6H2O (0.030 mmol, 13.0 mg) is substituted for Eu(NO3)3. Colorless flaky crystals were collected with the yield of 35% (based on Ce). Elemental analysis (%): calcd for C48H48Ce2O27: C, 43.07; H, 3.58. Found: C, 42.94; H, 3.55. IR (KBr pellet, cm-1): 3450 (vs), 1623 (vs), 1451 (vs), 1405 (vs), 976 (m), 967 (m), 869 (s), 762 (s), 753 (s), 695 (m), 643 (m).
Scheme 1. The bonding patterns of TPTC4- in CPs 1-4.
3. Results and Discussion 3.1 Descriptions of crystal structures 3.1.1 Structural description bimb)2]·4.5(H2O)}n (1)
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According to X-ray diffraction analysis, complex 1 belongs to the monoclinic system and P21/n space group. As can be seen
Fig. 2. (a) The bonding situation of the Cu(II) ions. (b) The 2D structure of 2. (c) The topological structure of 2.
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Analysis of crystal data showed that complex 4 belongs to the monoclinic system with C2/c space group. There are one Ce(III) ion, one TPTC4- linker, four coordination water molecules, half of 1,4-dioxane and half of the lattice water molecules in the repeating unit. As can be seen from Fig. 4a, Ce1 is coordinated with five O-atoms (O1i, O2i, O4, O7ii, O6iii) from four TPTC4ligands and four O-atoms (O1W, O2W, O3W, O4W) from four coordination water molecules. The Ce1–O separations vary from 2.517(2) Å to 2.582(2) Å, and the O–Ce1–O bond angles vary from 51.10(8) to 146.14(9) °. Ce(III) ions were linked by TPTC4ligands adopting the µ4-η2:η1:η1:η1 bonding mode (V) (Scheme 1) to form a 2D structure (Fig. 4b), which is further packed into 3D supramolecular structures (Fig. 4d) by H-bonding interaction involving the coordinated water molecules, lattice 1,4-dioxane molecules and uncoordinated oxygen atoms from ligands. The details of hydrogen bonds are listed in Table S3. Topologically, the 2D structure can be simplified as a 4-c network with the point symbol of {44.62} (Fig. 4c).
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Analysis of crystal data showed that complex 2 crystalizes in monoclinic system and C2/c space group, and the repeating unit consists of half of TPTC4− linkers, one 1,3-bimb linker and one Cu(II) ion. Cu1 ion is surrounded by two O-atoms (O1, O2) from two TPTC4− linkers and two N-atoms (N1, N3) from two different 1,3-bimb linkers, exhibiting a quadrilateral geometry (Fig. 2a). The Cu–N/O distances vary from 1.974(3) to 1.990(3) Å, and the O–Cu–O/N angles vary from 88.50(9) ° to 174.46(12) °, respectively. In 2, Cu(II) ions are connected with TPTC4- and 1,3-bimb ligands to form a 2D structure (Fig. 2b), in which the TPTC4- ligand adopts a bonding mode of µ4η1:η1:η1:η1 (Mode (II), Scheme 1). Topologically, the 2D structure can be simplified as a 4-c kgm type topology with the point symbol of {32.62.72} (Fig. 2c).
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Fig. 3. (a) The bonding situation of the Eu(III) ions (symmetry code: (vi) 1-x, 1-y, -z; (vii) 1-x, 1-y, -1-z; (viii) 2-x, 1-y, 1-z; (ix) 1-x, -y, 2-z; (x) x, 1+y, 1+z; (xi) -1+x, y, z; (xii) x, y, -1+z.). (b) The [Eu4(COO)12] cluster in 3. (c) The 3D network of 3. (d) The topology of 3.
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Analysis of crystal data indicated that complex 3 is attributed to the triclinic system with P-1 space group. The asymmetric unit of 3 consists of two Eu(III) ions, one and half of TPTC4− linkers, four coordinated water molecules, two lattice 1,4-dioxane molecules and four and half lattice water molecules. As can be seen from Fig. 3a, Eu1vi is coordinated with seven O-atoms (O4vi, O12vi, O3, O11vi, O10xiii, O4vi, O2viii) from five TPTC4− linkers and two O-atoms (O2Wvi, O3Wvi) from two lattice water molecules. Eu2xiii is surrounded by six O-atoms (O1viii, O9xiii, O6xv, O7xiv, O8xiv and O5xv) from the four TPTC4− ligands and two O-atoms (O4Wxiii, O5Wxiii) from two lattice water molecules. The Eu–O distances vary from 2.278(4) Å to 3.056(5) Å. The O– Eu–O angles vary from 52.18(14) ° to 153.32(16) °. In 3, four Eu(III) ions are linked by twelve carboxyl groups to form [Eu4(COO)12] SBUs (Fig. 3b), which were expanded by TPTC4ligands adopting the coordination modes of µ4-η2:η2:η2:η2 (III) and µ7-η1:η1:η2:η1:η1:η2:η1 (IV)(Scheme 1) to construct a complicated 3D structure (Fig. 3c). Topologically, when the tetranuclear [Eu4(COO)12] SBUs and TPTC4- ligands are taken as 12-connected nodes and 4-connectd nodes respectively, the
Fig. 4. (a) The coordination situation of the Ce(III) ions (symmetry code: (i) x, -y, 0.5+z; (ii) 1.5-x, 0.5+y, 1.5-z; (iii) x, -y, -0.5+z; (iv) 0.5+x, -0.5+y, z; (v) -0.5+x, 0.5+y, z; (vi) x, -1+y, z ). (b)The 2D network of 4 viewed on b axis perspective. (c) The topological structure of 4. (d) The 3D network of 4 formed by hydrogen-bonding.
3.2.2 Powder X-ray diffraction analyses (PXRD) and thermal analyses (TG). The PXRD diagrams of complexes 1-4 were shown in Fig. S1, and the pivotal peak positions of the measured PXRD patterns are almost the same as those of the simulated ones, demonstrating that the title complexes have good phase purity. Thermogravimetric measurements were carried out to check the thermal stability of 1-4 (Fig. S2). For 1, the weight loss of 7.52% (calcd: 7.45%) is assigned to the loss of four and a half lattice water molecules below 130 °C. The weight loss of 77.08% (calcd: 77.47%) is attributed to the loss of two 1,2-bimb ligands and a TPTC4- ligand between 290 and 500 °C. After that, its framework completely decomposes and the residue is CuO. As for 2, the framework begins to decompose above 260 °C and completely collapse at 650 °C. The residue is CuO of 16.58% (calcd:
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3.3 Fluorescent Properties
To check the recognition sensitivity of 1 for metal ions, a series of M(NO3)n solutions (0.01mol·L-1, M = Ag+, K+, Na+, Co2+, Ba2+, Pb2+, Ni2+, Cd2+, Cu2+, Mn2+, Al3+ and Fe3+) were selected as the analytes. The finely samples of 1 (2 mg) were ground and dissolved in 2 mL M@H2O suspension solution with the ultrasonic treatment for 30 min. As shown in Fig. 6, fluorescent intensity of Fe3+ for 1 was almost quenched by comparing with other metal ions, which indicated that 1 is sensitive to Fe3+ ions. In order to further explore the effect of the concentration gradient of Fe3+ on fluorescent intensity of 1, as exhibited in Fig. 7, the results showed that the fluorescent intensity of 1 gradually decreased to almost zero with the increasing Fe3+ concentration to be 0.125 mM. Nonlinear fitting of I0/I and the Fe3+ concentrations can be expressed by an exponential equation, where I0 and I are the fluorescent intensity of 1@H2O and 1@Mn+, respectively. It can be found that there is a linear Stern-Volmer equation (SV): (I0/I) = 1 + Ksv [M] at low concentration (Ksv and [M] represent the quenching constant and the concentration of metal ions (mM), respectively). The Ksv value was found to be 3.4 × 104 M−1, which is higher than that of the previously reported Eu-based CPs, for instance, MIL-53COOH (Al) (5.12 × 103 M−1), [Ln(cptpy)3]n (4.1 × 103 M−1) and Eu-MOF-LIC-1 (2.87 × 104 M−1) [37-39]. These results showed that complex 1 has good fluorescence sensitivity for Fe3+.The detection limit (2.5 × 10-4 M) was calculated by 3σ/Ksv (σ is the standard deviations for three cycles fluorescence tests of blank solutions at room temperature. The values of σ and exponential equation are in Table S4 and S5).
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The emission spectra of complexes 1 and 3, H4TPTC and 1,2bimb ligands were tested at room temperature in the solid state (Fig. 5). The maximum peaks of the H4TPTC and 1,2-bimb ligands are at 408 nm and 437 nm (λex=280 nm) respectively, which are derived from the electronic transitions of π-π* or π*n.[28-30]
617 nm is consistent with the previously reported Eu-based MOF.[1, 35, 36]
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15.91%). For 3, the weight loss of 12.32% (calcd: 12.37%) in the range of 60–150 °C corresponds to the loss of four and a half lattice water molecules and four coordination water molecules. The weight loss of 14.18% (calcd: 14.23%) is due to the loss of two 1,4-dioxane from 250 °C to 300 °C. The framework is stable until the temperature is up to 390 °C. As for 4, the weight loss of 19.25% (calcd: 19.28%) under 274 °C is assigned to the loss of four coordination water molecules, half of lattice 1,4-dioxane molecules and half of lattice water molecules. The framework begins to collapse beyond 450 °C.
Fig. 5. Solid fluorescence spectra of complexes 1 and 3, H4TPTC and 1,2-bimb ligands.
Compared to H4TPTC ligand, the maximum emission peak of 1 at 328 nm is blue-shifted by 80 nm, which may be that the bonding modes between metal ions and ligands increase effectively the rigidity of complexes and reduce the loss of nonradiative energy.[32-34] As for 3, the characteristic emission peaks are at 536 nm, 590 nm, 617 nm respectively, which are attributed to electronic transitions (5D0-7FJ, J=0-4) of Eu3+ ion, respectively (Fig. 5). Especially, the strongest characteristic emission peak at
Fig. 6. The fluorescence intensity of complex 1 which were dispersed in M(NO3)n solutions.
Furthermore, inspired by the experiments of metal ions, the recognition sensitivity of anions was also tested. The experimental procedures were similar to those of metal ions except for replacing M(NO3)n with KnX (0.01 mol·L-1, X = Cl-, Br-, I-, SCN-, H2PO4-, HCO3-, CO32-, NO3-, SO42-, C2O42- and Cr2O72-). As exhibited in Fig. S3, fluorescence intensity of 1 was almost completely quenched by Cr2O72- ion compared with other anions. As the calculation method of metal ions, the value of Ksv and the detection limit were calculated to be 4.9×104 M−1 and 1.8 × 10-4 M, respectively, which is larger than the previously reported. [40] The PXRD patterns of samples after fluorescence tests are almost the same as the simulated ones (Fig. S4), which indicate that complex 1 is stable and don’t have coordination with ions. The possible reason of fluorescence quenching is that the
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Ksv value and the detection limit are found to be 1.0 × 104 M−1 and 6.2 × 10-4 M, respectively. The possible quenching mechanism of NDVs for 3 is attributed to the energy transfer between the electron-rich complex 3 and the electron-deficient NDVs. [42] In addition, there are energy competitive absorption between complex and the analyte, which can be verified by the UV-visible absorption studies. The results show that there are an obvious overlap between the UV-visible absorption spectra of NDVs and the excitation spectrum of 1 (Fig. S8).
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In summary, four novel complexes have been synthesized based on rigid terphenyl-3,3",5,5"-tetracarboxylic acid under solvothermal methods. The experimental results showed complex 1 has good fluorescence sensitivity for Fe3+ and Cr2O72- ions in aqueous solutions, which shows it has the potential as a dualfunctional detecting sensor for Fe3+ and Cr2O72- ions with low detection limits. Complex 3 has obvious detection sensitivity for NDVs. Moreover, the detecting mechanisms are also discussed. These results provide theoretical and experimental guidance for the further synthesis of fluorescence recognition materials with excellent properties.
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Acknowledgements
Fig. 7. Fluorescence spectra of complex 1 in aqueous solutions with the concentration of Fe3+ increase. Inset: nonlinear fitting of fluorescence quenching and linear fitting at low concentration.
The authors gratefully acknowledge the National Natural Science Foundation of China (No: 21676258), the international Scientific and Technological Cooperation Projects of Shanxi Province (No: 201803D421080) and the support of innovative research team of inorganic-organic hybrid functional materials in North University of China.
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Appendix A. Supplementary data
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Fig. 8. Fluorescence spectra of complex 3 in DMF as the concentration of NT increase. Inset: linear fitting of fluorescence quenching at low concentration.
Interestingly, as it is exhibited in Fig. S6 that complex 3 has obvious recognition sensitivity for nitrobenzene. Thus, the sensing experiments of 3 for other nitrobenzene derivatives (NDVs) (nitrobenzene (NB), p-nitroaniline (NA), p-nitrotoluene (NT), and p-nitrophenol (NP)) were also carried out. The results showed that the quenching efficiency of NDVs for 3 is NT>NA>NB>NP, and the quenching rate reached 98% when the concentration of NT was 1.5 mM (Fig. S7 and Fig. 8). The quenching constant can be expressed with the SV equation: (I0/I) = 1 + Ksv [M], where I0 and I are fluorescence intensities of 3 in blank DMF solution and upon adding NDVs, respectively. At low concentrations, the SV plot for NT is nearly linear, and the
The Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies of the data can be obtained free of charge on quoting the depository numbers CCDC 1882252, 1882253, 1882521, 1882254 (Fax: +44-1223-33-033; E-Mail: [email protected], http://www.ccdc. cam. ac.uk).
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Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Highlights:
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(1) Four novel complexes have been synthesized based on rigid terphenyl-3,3",5,5"-tetracarboxylic acid by solvothermal methods.
(2) The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity
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for Fe3+ and Cr2O72- ions in aqueous solutions, and 3 can selectively detect NDVs.
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Structural Diversity and Fluorescent Sensing of Four Novel Complexes Based on Rigid terphenyl-3,3",5,5"-tetracarboxylic acid Jinxia Lianga, Qiannan Zhaoa, Lingling Gaoa, Jie Zhanga, Xiaoyan Niua, and Tuoping Hua*
Synopsis:
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Four novel complexes have been synthesized based on rigid terphenyl-3,3",5,5"-tetracarboxylic acid by solvothermal methods. The fluorescent properties of complexes 1 and 3 showed that 1 has good fluorescence sensitivity for Fe3+ and Cr2O72- ions in aqueous solutions, and 3 can selectively detect NDVs.
Journal Name,1 [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]
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2 ournal Name, [year], [vol], 00–00This journal is © The Royal Society of Chemistry [year]
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