

基于咪唑衍生物和2,5-二甲氧基对苯二甲酸的Zn(Ⅱ)-MOFs的合成、晶体结构和荧光性质
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关键词:
- 金属有机骨架
- / 咪唑衍生物配体
- / 2,5-二甲氧基对苯二甲酸
- / 穿插结构
- / 荧光性质
English
Three Zn(Ⅱ)-MOFs Based on Imidazole Derivatives and 2, 5-Dimethoxyterephthalic Acid: Syntheses, Crystal Structures, and Fluorescence Properties
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0. Introduction
Metal-organic frameworks (MOFs) not only show exquisite microstructures and topology diversity[1-3] but also have many potential applications in gas storage and separation, catalysis, luminescence sensing, drug delivery, etc[4-7]. Given these favorable characteristics, syntheses of MOFs have become a research hotspot in the fields of inorganic chemistry and materials science. Because MOFs are constructed by metal ions/clusters and organic ligands[8], the inherent properties of carefully designed/selected metal ions and organic ligands can endow MOFs with some unique functions[9-11]. For example, the photoluminescent properties of MOFs can be adjusted by changing the metal centers and ligands in the hybrid system[12].
However, the final structures of MOFs are affected by many reaction factors, such as solvent system, ligand structure, temperature, pH, and metal ions species. Therefore, it is difficult to synthesize MOFs with excellent structure[13]. Fortunately, organic ligands play a key role in the process of synthesizing MOFs. Among a variety of organic ligands, aromatic polycarboxylic acid and nitrogen heterocyclic ligands have a strong coordination ability with metal ions[14-15]. So, it is a good choice to obtain target MOFs by using different nitrogen heterocyclic derivatives and aromatic carboxylic acids as ligands.
As one of the aromatic carboxylic acids, 2, 5-dimethoxyterephthalic acid (H2DTA) is an effective linker for its own advantages: (1) two rigid carboxylate groups indicate rich coordination sites; (2) two methoxy groups as electron-donating groups can increase the nucleophilicity of ligand[16-17]. Based on aforementioned search backgrounds, H2DTA was selected to help midazole derivatives 1, 2, 4, 5-tetra(1H-imidazol-1-yl)benzene (1, 2, 4, 5-TIB), 1, 4-bis(4-methyl-1H-imidazol-1-yl) benzene (1, 4-BMIB) and 1, 4-bis(4-methyl-1H-imidazol-1-yl)naphthalene (1, 4-BMIN) to assemble with Zn(Ⅱ) to build MOFs (Scheme 1). As a result, three 3D (three-dimensional) MOFs, namely {[Zn(DTA)(1, 2, 4, 5-TIB)0.5]·1.5H2O}n (1), [Zn(DTA)(1, 4-BMIB)0.5(H2O)]n (2), and {[Zn(DTA) (1, 4-BMIN)] ·H2O}n (3), were prepared under solvothermal condition. Herein, their syntheses, structures, and fluorescence properties are reported.
Scheme 1
1. Experimental
1.1 Reagents and instruments
All chemicals were commercially available and used without further purification. Powder X-ray diffraction (PXRD) patterns were performed on a Rigaku MiniFlex 600 diffractometer (Voltage: 40 kV, Current: 15 mA, Cu Kα radiation, λ=0.154 060 nm) in a range of 5.00° to 50.00°. Thermogravimetric analyses (TGA) data were collected by a NETSCHZ STA-F3 thermoanalyzer from room temperature to 800 ℃, respectively. IR spectra were measured as KBr pellets from 400 to 4 000 cm-1 on a Tianjin Gangdong 7600 FT-IR spectrometer.
1.2 Synthesis of MOF 1
Zn(BF4)2·6H2O (36 mg, 0.15 mmol), H2DTA (22 mg, 0.10 mmol), and 1, 2, 4, 5-TIB (34 mg, 0.10 mmol) were dissolved in a mixed solvent of H2O (4 mL) and N, N-dimethylformamide (1 mL). Then, the resulting solution was stirred for 30 min and put into a 20 mL glass vial, and heated at 80 ℃ for 3 d. The colorless block crystals were obtained and washed with ethanol and dried in the air with a yield of 35% (based on H2DTA). Anal. Calcd. for C19H18N4O7.5Zn(%): C, 46.79; H, 3.72; N, 11.49. Found(%): C, 45.83; H, 3.58; N, 11.62. IR (KBr pellet, cm-1): 3 408m, 3 107w, 3 017w, 1 592s, 1 530s, 1 488s, 1 460m, 1 403m, 1 257m, 1 348s, 1 232m, 1 208s, 1 068m, 1 034m, 985w, 935w, 859w, 817w, 796w, 761w, 650w, 629w, 530w.
1.3 Synthesis of MOF 2
Zn(NO3)2·6H2O (45 mg, 0.15 mmol), H2DTA (22 mg, 0.10 mmol), and 1, 4-BMIB (23 mg, 0.10 mmol) were placed in a 5 mL mixed solvent of N, N-diethylformamide (DEF) and H2O (4∶1, V/V) and stirred for 10 min. Then, the resulting solution was heated at 100 ℃ for 3 d. The colorless block crystals of 2 were obtained with a yield of 53% (based on H2DTA). Anal. Calcd. for C17H17N2O7Zn(%): C, 47.85; H, 4.02; N, 6.57. Found (%): C, 47.36; H, 3.91; N, 6.74. IR (solid KBr pellet, cm-1): 3 491m, 3 129w, 2 947w, 1 586s, 1 522m, 1 494m, 1 439m, 1 411s, 1 348s, 1 285m, 1 243m, 1 208s, 1 135w, 1 027m, 887w, 845w, 748w, 650w, 552w.
1.4 Synthesis of MOF 3
Zn(NO3)2·6H2O (45 mg, 0.15 mmol), H2DTA (22 mg, 0.10 mmol), and 1, 4-BMIN (28 mg, 0.10 mmol) were placed in a 4 mL mixed solvent of DEF, H2O, and methanol (2∶1∶1, V/V) and stirred for 30 min. The final suspending solution was put into a 20 mL glass vial and heated at 100 ℃ for 3 d. The colorless block crystals of 3 were obtained with a yield of 61% (based on H2DTA). Anal. Calcd. for C28H26N4O7Zn(%): C, 56.44; H, 4.40; N, 9.40. Found(%): C, 57.56; H, 4.23; N, 9.45. IR (solid KBr pellet, cm-1): 3 477w, 3 101w, 2 954w, 2 921w, 2 836w, 1 600s, 1 502w, 1 439m, 1 389m, 1 341m, 1 278s, 1 208s, 1 174w, 1 124w, 1 027m, 935w, 845w, 775m, 754m, 664w, 636w, 440w.
1.5 Determination of the structure
The data of three single crystals with dimensions of 0.2 mm×0.1 mm×0.1 mm (1), 0.20 mm× 0.20 mm× 0.20 mm (2), and 0.30 mm×0. 2 mm×0.20 mm (3) were obtained on a Rigaku 003 CCD diffractometer with a Mo Kα radiation (λ =0.071 073 nm) at room temperature, respectively. Their structures were solved via the SHELXT-2014 program and refined by SHELXL-2017 on Olex2-1.2 software[18-19]. All non-hydrogen atoms were refined anisotropically. The H atoms from C atoms were positioned geometrically and disposed of by using a riding model, and the H atoms from H2O moieties were located by difference maps and constrained to ride on their parent O atoms. The crystal data and refinement parameters for 1, 2, and 3 are summarized in Table 1, and some selected bond lengths and angles are listed in Table S1 (Supporting information).
Table 1
Parameter 1 2 3 Empirical formula C19H15N4O6Zn·1.5H2O C17H17N2O7Zn C28H24N4O6Zn·H2O Formula weight 487.75 426.69 595.92 Crystal system Monoclinic Monoclinic Monoclinic Space group P21/n P21/n P21/c a/nm 1.187 94(5) 1.026 42(9) 1.198 15(6) b/nm 1.180 15(4) 1.753 97(12) 1.630 54(11) c/nm 1.499 29(5) 1.045 28(10) 1.414 81(8) β/(°) 90.311(3) 111.330(11) 100.294(5) Volume/nm3 2.101 89(13) 1.752 9(3) 2.719 5(3) Temperature/K 295.2 295.2 295.2 Z 4 4 4 Dc/(g·cm-3) 1.570 1.617 1.411 μ/mm-1 1.211 1.445 0.952 F(000) 940.0 876.0 1192.0 θmin, θmax/(°) 3.655, 30.333 4.066, 30.420 3.676, 30.297 Limiting indices -16≤h≤16,
-16≤k≤16,
-21≤l≤20-14≤h≤14,
-24≤k≤24,
-14≤l≤13-16 ≤ h ≤ 16,
-22 ≤ k ≤ 20,
-19 ≤ l ≤ 19Reflection collected, unique 44 158, 5 888 19 114, 4 786 34 674, 7 368 Data, restraint, parameter 5 888, 6, 273 4 786, 2, 255 7 368, 15, 374 Goodness-of-fit on F2 0.984 1.034 1.000 Final R indices [I>2σ(I)] R1=0.039 3, wR2=0.103 1 R1=0.042 5, wR2=0.105 2 R1=0.051 2, wR2=0.123 2 Final R indices (all data) R1=0.054 4, wR2=0.108 4 R1=0.058 7, wR2=0.112 9 R1=0.067 8, wR2=0.131 1 (Δρ)max, (Δρ)min/(e·nm-3) 670, -460 700, -620 1 110, -570 CCDC: 2129603, 1; 2129604, 2; 2129604, 3.
2. Results and discussion
2.1 Crystal structure of 1
Single-crystal X-ray diffraction reveals that complex 1 crystallizes in the monoclinic system with the P21/n space group. The asymmetric unit of 1 contains one Zn(Ⅱ) ion, one DTA2- ion, and half a 1, 2, 4, 5-TIB molecule. Additionally, some disordered guest molecules in the asymmetric unit could not be further identified, so their reflection data have to be subtracted from the corresponding single crystal structure by the SQUEEZE method[20]. Even so, one and a half guest water molecules should exist in the asymmetric unit according to SQUEEZE information, elemental analysis result, and thermogravimetric data. The Zn(Ⅱ) ion center adopts a slightly distorted tetrahedral configuration to coordinate with two carboxyl oxygen atoms from two DTA2- ions and two nitrogen atoms from two imidazole groups of 1, 2, 4, 5-TIB molecules (Fig. 1a). If only 1, 2, 4, 5-TIB molecules and Zn(Ⅱ) ions are considered, 1, 2, 4, 5-TIB molecules and Zn(Ⅱ) ion centers build a 2D layer parallel to the crystallographic bc plane (Fig. 1b). Zn(Ⅱ) ion centers are further connected by DTA2- ions, forming a classical pillared-layer framework (Fig. 1c). In the framework, the Zn(Ⅱ) center acts as a four-connected node, while the DTA2- and 1, 2, 4, 5-TIB ligands are only simple connectors. Therefore, the whole framework can be considered as a four-connected net with a point symbol of (62.84) from a topology view (Fig. 1d)[21].
Figure 1
Figure 1. Crystal structure of 1: (a) coordination environment of Zn(Ⅱ); (b) perspective of 2D 1, 2, 4, 5-TIB-Zn(Ⅱ) layer parallel to the bc plane; (c) 3D pillared-layer framework; (d) 4-connected netEllipsoid probability level: 50%; Symmetry codes: a: 0.5+x, 0.5-y, -0.5+z; b: -0.5+x, 1.5-y, -0.5+z; c: 1-x, 2-y, 1-z
2.2 Crystal structure of 2
Complex 2 also belongs to the monoclinic space group P21/n. The asymmetric unit is comprised of a Zn(Ⅱ) ion, a DTA2- anion, half a 1, 4-BMIB molecule, and a lattice water molecule. It′s important to note that two carboxyl groups from DTA2- indicate different coor-dination modes, where one carboxyl group is connected by a Zn(Ⅱ) ion and another carboxyl group is connected by two Zn(Ⅱ) ions. Hence, DTA2- is a μ3-linker connected by three Zn(Ⅱ) ions. For such coordination mode in DTA2-, a binuclear Zn (Zn1, Zn1a) unit Zn2(CO2)4 is formed (Fig. 2a). In the unit Zn2(CO2)4, Zn(Ⅱ) adopts a five-coordinate geometry of distorted trigonal bipyramid to coordinate with three carboxyl O atoms, an imidazole N atom, and a water molecule. Each Zn2(CO2)4 unit is connected by four DTA2- ions, resulting in a 2D Zn-DTA layer parallel to the crystallographic ab plane (Fig. 2b). 2D Zn-DTA layers are further connected together by 1, 4-BMIB ligands to form a 3D framework (Fig. 2c). Difference from 1, 2, 4, 5-TIB, 1, 4-BMIB is a slim ligand with low coordination numbers. For this reason, structural interpenetration is difficult to avoid. In fact, the 3D framework of complex 2 is a 2-fold interpenetration structure (Fig. 2d). In complex 2, each Zn2(CO2)4 unit acts as a six-connected node, while DTA2- and 1, 4-BMIB ligands are simple linkers. Therefore, the whole framework of complex 2 is a six-connected pcu -type net with a point symbol of (412.63) (Fig.S4)[22].
Figure 2
Figure 2. Crystal structure of 2: (a) coordination environment of binuclear unit Zn2(CO2)4; (b) perspective of 2D Zn-DTA layer parallel to ab plane; (c) 3D framework constructed by Zn-DTA layers and 1, 4-BMIB ligands; (d) 2-fold-interpenetrating structureEllipsoid probability level: 50%; Symmetry codes: a: 1-x, 1-y, -z; b: 1.5-x, 0.5+y, 0.5-z; c: 0.5+x, 1.5-y, 0.5+z; d: -x, 1-y, 1-z; e: 1.5-x, -0.5+y, 0.5-z; f: -0.5+x, 1.5-y, -0.5+z
2.3 Crystal structure of 3
Complex 3 crystallizes in the monoclinic system with space group P21/c. The corresponding asymmetric unit is composed of one Zn2+ ion, two-half DTA2- ions, and one 1, 4-BMIN molecule. Some disordered guest molecules also exist in complex 3, which also have been disposed of by the SQUEEZE method[21]. Based on the SQUEEZE information, elemental analysis result, and thermogravimetric data, each asymmetric unit in complex 3 should contain a disordered guest water molecule. Just as Zn(Ⅱ) ion in complex 1, the Zn(Ⅱ) ion is still a slightly distorted {ZnO2N2} tetrahedral sphere, surrounded by two carboxylate O atoms from two DTA2- anions and two N atoms from two 1, 4-BMIN molecules (Fig. 3a). DTA2- and 1, 4-BMIN ligands connect the Zn(Ⅱ) ion centers together to obtain a 3D framework (Fig. 3b), which is a triple-interleaved dia-type network with a point symbol of (66) (Fig. 3c and 3d)[22].
Figure 3
2.4 PXRD patterns and TGA
The PXRD of 1-3 was performed at room temperature to check their phase purity. As shown in Fig. 4a, the test PXRD patterns match well with the simulated ones, indicating the phase purity of complexes 1, 2, and 3 (Fig. 4a). To further investigate their thermal stabilities, the TGA experiments for 1-3 were carried out from room temperature to 800 ℃ under a nitrogen atmosphere (Fig. 4b). The TGA curve of 1 indicated the first weight loss of 6.0% from room temperature to 110 ℃, which should be attributed to the release of one and a half disorder water molecules in each asymmetric unit (Calcd. 5.6%). After 300 ℃, rapid weight loss continued until the end of the experiment. Complex 2 indicated an about 4.5% weight loss from the beginning to 120 ℃, which mainly corresponds to the loss of coordination water molecules (Calcd. 4.2%). The curve between 120 and 379 ℃ was almost a straight line, revealing that complex 2 is very stable in this temperature range. After 379 ℃, the TGA curve droped sharply until the end of the experiment. Complex 3 displayed a 3.1% weight loss before 120 ℃, confirming that each asymmetric unit contains a guest water molecule (Calcd. 3.0%). As the temperature further increased, the framework began to collapse from 320 ℃.
Figure 4
2.5 UV-Vis and luminescent properties
The solid UV-Vis absorption spectra of complexes 1-3 are shown in Fig. 5a. In the UV region between 200 and 400 nm, all complexes had two maximum absorption peaks at 260 and 325 nm, respectively. These characteristic absorption peaks should be attributed to the π-π* transition between the ligands and metal ions[23].
Figure 5
Considering d10 metal inorganic-organic hybrid coordination polymers with excellent luminescent properties, their fluorescence tests were performed (Fig. 5b). Under the excitation light with a wavelength of 275 nm, H2DTA had a maximum emission peak at 410 nm. In contrast, the emission bands of the three complexes were stronger than that of the ligand, and the maximum emission peaks for complexes 1-3 were 398 nm (λex=340 nm), 385 nm (λex=328 nm), and 393 nm (λex=281 nm), respectively. Compared to the emission peak of H2DTA, all complexes had a blue shift phenomenon, which may be caused by the intraligand (n-π* or π-π*) transition. The enhanced luminescence of complexes 1-3 should be attributed to the combination of the ligand and the metal center, reducing the energy loss caused by non-radiation attenuation[24].
3. Conclusions
In summary, different imidazole derivatives as linkers were introduced to assemble with Zn(Ⅱ) ions to obtain three 3D MOFs. Complexes 1, 2, and 3 are a four-connected net, a six-connected pcu-type net with a 2-fold interpenetration structure, and a triple-interleaved dia-type network, respectively. The rigid imidazole derivatives play a key role in constructing complexes with different structures. Moreover, compared with the fluorescence of H2DTA, the fluorescence of the three complexes was enhanced and the blue shift occurred.
Supporting information is available at http://www.wjhxxb.cn
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[1]
Zhan D Y, Saeed A, Li Z X, Wang C M, Yu Z W, Wang J F, Zhao N J, Xu W H, Liu J H. Highly Fluorescent Scandium-Tetracarboxylate Frameworks: Selective Detection of Nitro-Aromatic Compounds, Sensing Mechanism, and Their Application[J]. Dalton Trans., 2020, 49(48): 17737-17744. doi: 10.1039/D0DT03781H
-
[2]
Gao M L, Cao X M, Zhang Y Y, Qi M H, Wang S M, Liu L, Han Z B. A Bifunctional Luminescent Europium-Organic Framework for Highly Selective Sensing of Nitrobenzene and 4-Aminophenol[J]. RSC Adv., 2017, 7(71): 45029-45033. doi: 10.1039/C7RA08885J
-
[3]
Hu Z C, Pramanik S, Tan K, Zheng C, Liu W, Zhang X, Chabal Y J, Li J. Selective, Sensitive, and Reversible Detection of Vapor-Phase High Explosives via Two-Dimensional Mapping: A New Strategy for MOF Based Sensors[J]. Cryst Growth Des., 2013, 13(10): 4204-4207. doi: 10.1021/cg4012185
-
[4]
Kaur R, Paul A, Deep A. Highly Sensitive Chemosensing of Trinitrotoluene with Europium Organic Framework/Gold Nanoparticle Composite[J]. Inorg. Chem. Commun., 2014, 43: 118-120. doi: 10.1016/j.inoche.2014.02.025
-
[5]
Roales J, Moscoso F G, Gámez F, Lopes-Costa T, Sousaraei A, Casado S, Castro-Smirnov J R, Cabanillas-Gonzalez J, Almeida J, Queirós C, Cunha-Silva L, Silva A M G, Pedrosa J M. Preparation of Luminescent Metal-Organic Framework Films by Soft-Imprinting for 2, 4-Dinitrotoluene Sensing[J]. Materials, 2017, 10(9): 992. doi: 10.3390/ma10090992
-
[6]
Wu Y, Li Y L, Wu X R, Luo M M, Zou L K, Xu Q X, Cai S G. An Uncommon 3D (3, 8)-Connected Metal-Organic Framework: Luminescence Sensing and Photocatalytic Properties[J]. J. Solid State Chem., 2018, 262: 256-263. doi: 10.1016/j.jssc.2018.03.031
-
[7]
Du Z Q, Li Y P, Wang X X, Wang J, Zhai Q G. Enhanced Electrochemical Performance of Li-Co-BTC Ternary Metal-Organic Frameworks as Cathode Materials for Lithium-Ion Batteries[J]. Dalton Trans., 2019, 48(6): 2013-2018. doi: 10.1039/C8DT04863K
-
[8]
Qu X L, Gui D, Zheng X L, Li R, Han H L, Li X, Li P Z. A Cd-Based Metal-Organic Framework as a Luminance Sensor to Nitrobenzene and Tb(Ⅲ) Ion[J]. Dalton Trans., 2016, 45(16): 6983-6989. doi: 10.1039/C6DT00162A
-
[9]
Sowmehesaraee M S, Ranjbar M, Abedi M, Mozaffari S A. Fabrication of Lead Iodide Perovskite Solar Cells by Incorporating Zirconium, Indium and Zinc Metal-Organic Frameworks[J]. Sol. Energy, 2021, 214: 138-148. doi: 10.1016/j.solener.2020.12.001
-
[10]
Goswami R, Seal N, Dash S R, Tyagi A, Neogi S. Devising Chemically Robust and Cationic Ni(Ⅱ)-MOF with Nitrogen-Rich Micropores for Moisture-Tolerant CO2 Capture: Highly Regenerative and Ultrafast Colorimetric Sensor for TNP and Multiple Oxo-Anions in Water with Theoretical Revelation[J]. ACS Appl. Mater. Interfaces, 2019, 11(43): 40134-40150. doi: 10.1021/acsami.9b15179
-
[11]
Mohanty A, Singh U P, Butcher R J, Das N, Roy P. Synthesis of Fluorescent MOFs: Live-Cell Imaging and Sensing of a Herbicide[J]. CrystEngComm, 2020, 22(26): 4468-4477. doi: 10.1039/D0CE00490A
-
[12]
Shi Z Q, Ji N N, Hu H L. Luminescent Triphenylamine-Based Metal-Organic Frameworks: Recent Advances in Nitroaromatics Detection[J]. Dalton Trans., 2020, 49(37): 12929-12939. doi: 10.1039/D0DT02213F
-
[13]
Gheorghe A, Imaz I, Vlugt J I V D, Maspoch D, Tanase S. Tuning the Supramolecular Isomerism of MOF-74 by Controlling the Synthesis Conditions[J]. Dalton Trans., 2019, 48(27): 10043-10050. doi: 10.1039/C9DT01572H
-
[14]
Li J, Zhao Z X, Liu T, Gong Z F, Jin Y H, Sun L B, Qi M. Cu(Ⅱ)-Based Coordination Polymers: Protective Effect on Suppurative Lymphadenitis by Regulating miR-155 and miR -34a Expression in the Lymph Node Cells[J]. J. Coord. Chem., 2021, 74(9): 1673-1682.
-
[15]
Wang Y, Zeng H M, Mao W T, Wang X J, Jiang Z G, Zhan C H, Feng Y L. The Synthesis and Photoluminescence of Three Porous Metal-Organic Frameworks[J]. Inorg. Chem. Commun., 2021, 129: 108613. doi: 10.1016/j.inoche.2021.108613
-
[16]
Böhle T, Eissmann F, Weber E, Mertens F O R L. Poly[(μ4-2, 5-dimethoxybenzene-1, 4-dicarboxylato)manganese(Ⅱ)] and Its Zinc(Ⅱ) Analogue: Three-Dimensional Coordination Polymers Containing Unusually Coordinated Metal Centres[J]. Acta Crystallogr. Sect. C, 2011, C67: 5-8.
-
[17]
Guo Z G, Reddy M V, Goh B M, San A K P, Bao Q, Loh K P. Electrochemical Performance of Graphene and Copper Oxide Composites Synthesized from a Metal-Organic Framework (Cu-MOF)[J]. RSC Adv., 2013, 3(41): 19051-19056. doi: 10.1039/c3ra43308k
-
[18]
Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K, Puschmann H. OLEX2: A Complete Structure Solution, Refinement and Analysis Program[J]. J. Appl. Crystallogr., 2009, 42: 339-341. doi: 10.1107/S0021889808042726
-
[19]
Sheldrick G M. Crystal Structure Refinement with SHELXL[J]. Acta Crystallogr. Sect. C, 2015, C71: 3-8.
-
[20]
Spek A L. PLATON SQUEEZE: A Tool for the Calculation of the Disordered Solvent Contribution to the Calculated Structure Factors[J]. Acta Crystallogr. Sect. C, 2015, C71: 9-18.
-
[21]
Aexandrov E V, Blatov V A, Kochetkov A V, Proserpio D M. Underlying Nets in Three-Periodic Coordination Polymers: Topology, Taxonomy and Prediction from a Computer-Aided Analysis of the Cambridge Structural Database[J]. CrystEngComm, 2011, 13(12): 3947-3958. doi: 10.1039/c0ce00636j
-
[22]
Cui Y, Yue Y, Qian G, Cheng B L. Luminescent Functional Metal-Organic Frameworks[J]. Chem. Rev., 2012, 112(2): 1126-1162. doi: 10.1021/cr200101d
-
[23]
唐龙, 付宇豪, 王一彤, 王欢欢, 王记江, 侯向阳, 王潇. 利用2, 2'-氧基双(苯甲酸)和含N配体构筑的三个配合物的合成、结构与荧光性能[J]. 无机化学学报, 2020,36,(8): 1550-1556. TANG L, FU Y H, WANG Y T, WANG H H, WANG J J, HOU X Y, WANG X. Three Complexes Constructed Using 2, 2′ -Oxybis(benzoic acid) and N-Donor Ligands: Syntheses, Structures and Fluorescent Properties[J]. Chinese J. Inorg. Chem., 2020, 36(8): 1550-1556.
-
[24]
黎彧, 曾福燃, 周峰, 李善吉. 由醚氧桥联羧酸配体构筑的铜(Ⅱ)、锌(Ⅱ)和锰(Ⅱ)配位聚合物的合成、晶体结构、荧光及光催化性质[J]. 无机化学学报, 2020,36,(11): 2124-2134. doi: 10.11862/CJIC.2020.243LI Y, ZENG F R, ZHOU F, LI S J. Syntheses, Crystal Structures, Luminescence and Photocatalytic Activity of Cu(Ⅱ), Zn(Ⅱ) and Mn(Ⅱ) Coordination Polymers Based on Ether-Bridged Carboxylic Acids[J]. Chinese J. Inorg. Chem., 2020, 36(11): 2124-2134. doi: 10.11862/CJIC.2020.243
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[1]
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Figure 1 Crystal structure of 1: (a) coordination environment of Zn(Ⅱ); (b) perspective of 2D 1, 2, 4, 5-TIB-Zn(Ⅱ) layer parallel to the bc plane; (c) 3D pillared-layer framework; (d) 4-connected net
Ellipsoid probability level: 50%; Symmetry codes: a: 0.5+x, 0.5-y, -0.5+z; b: -0.5+x, 1.5-y, -0.5+z; c: 1-x, 2-y, 1-z
Figure 2 Crystal structure of 2: (a) coordination environment of binuclear unit Zn2(CO2)4; (b) perspective of 2D Zn-DTA layer parallel to ab plane; (c) 3D framework constructed by Zn-DTA layers and 1, 4-BMIB ligands; (d) 2-fold-interpenetrating structure
Ellipsoid probability level: 50%; Symmetry codes: a: 1-x, 1-y, -z; b: 1.5-x, 0.5+y, 0.5-z; c: 0.5+x, 1.5-y, 0.5+z; d: -x, 1-y, 1-z; e: 1.5-x, -0.5+y, 0.5-z; f: -0.5+x, 1.5-y, -0.5+z
Table 1. Crystallographic data and refinement parameters for MOFs 1-3
Parameter 1 2 3 Empirical formula C19H15N4O6Zn·1.5H2O C17H17N2O7Zn C28H24N4O6Zn·H2O Formula weight 487.75 426.69 595.92 Crystal system Monoclinic Monoclinic Monoclinic Space group P21/n P21/n P21/c a/nm 1.187 94(5) 1.026 42(9) 1.198 15(6) b/nm 1.180 15(4) 1.753 97(12) 1.630 54(11) c/nm 1.499 29(5) 1.045 28(10) 1.414 81(8) β/(°) 90.311(3) 111.330(11) 100.294(5) Volume/nm3 2.101 89(13) 1.752 9(3) 2.719 5(3) Temperature/K 295.2 295.2 295.2 Z 4 4 4 Dc/(g·cm-3) 1.570 1.617 1.411 μ/mm-1 1.211 1.445 0.952 F(000) 940.0 876.0 1192.0 θmin, θmax/(°) 3.655, 30.333 4.066, 30.420 3.676, 30.297 Limiting indices -16≤h≤16,
-16≤k≤16,
-21≤l≤20-14≤h≤14,
-24≤k≤24,
-14≤l≤13-16 ≤ h ≤ 16,
-22 ≤ k ≤ 20,
-19 ≤ l ≤ 19Reflection collected, unique 44 158, 5 888 19 114, 4 786 34 674, 7 368 Data, restraint, parameter 5 888, 6, 273 4 786, 2, 255 7 368, 15, 374 Goodness-of-fit on F2 0.984 1.034 1.000 Final R indices [I>2σ(I)] R1=0.039 3, wR2=0.103 1 R1=0.042 5, wR2=0.105 2 R1=0.051 2, wR2=0.123 2 Final R indices (all data) R1=0.054 4, wR2=0.108 4 R1=0.058 7, wR2=0.112 9 R1=0.067 8, wR2=0.131 1 (Δρ)max, (Δρ)min/(e·nm-3) 670, -460 700, -620 1 110, -570 -

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