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2017 Volume 34 Issue 9
2017, 34(9): 977-978
doi: 10.11944/j.issn.1000-0518.2017.09.170253
Abstract:
2017, 34(9): 979-995
doi: 10.11944/j.issn.1000-0518.2017.09.170182
Abstract:
Size and shape controlled growth of nano or micron sized metal-organic frameworks(MOFs) has attracted great attention in recent years. The ability to deliberately access monodisperse nano or microsized MOFs offers prospective applications in heterogeneous catalysis, porous membranes, thin-film devices, controlled drug release, and biomedical fields. This review highlights the recent development of size and shape controlled growth as well as the application of nano or micron sized MOFs, finally the future prospective is briefly addressed.
Size and shape controlled growth of nano or micron sized metal-organic frameworks(MOFs) has attracted great attention in recent years. The ability to deliberately access monodisperse nano or microsized MOFs offers prospective applications in heterogeneous catalysis, porous membranes, thin-film devices, controlled drug release, and biomedical fields. This review highlights the recent development of size and shape controlled growth as well as the application of nano or micron sized MOFs, finally the future prospective is briefly addressed.
2017, 34(9): 996-1005
doi: 10.11944/j.issn.1000-0518.2017.09.170177
Abstract:
Metal-Organic frameworks(MOFs) have been applied in rechargeable lithium ion batteries due to their high surface areas and tunable structures. We reviewed the recent progresses on MOFs as negative and positive electrodes for Li-ion battery. The state-of-the-art results and problems to be faced are also summarized. The perspective of using metal-organic frameworks is prospected for the future material innovation in electrochemical energy storage.
Metal-Organic frameworks(MOFs) have been applied in rechargeable lithium ion batteries due to their high surface areas and tunable structures. We reviewed the recent progresses on MOFs as negative and positive electrodes for Li-ion battery. The state-of-the-art results and problems to be faced are also summarized. The perspective of using metal-organic frameworks is prospected for the future material innovation in electrochemical energy storage.
2017, 34(9): 1006-1016
doi: 10.11944/j.issn.1000-0518.2017.09.170185
Abstract:
Metal-organic frameworks(MOFs) are a new class of porous materials formed by the self-assembly of metal ions(or metal clusters) and organic ligands. Currently, the application of metal-organic frameworks in separation of light hydrocarbons including methane, acetylene, ethylene, ethane, propylene and propane has attracted tremendous interests. This article briefly reviews the latest development in this field, and discusses the factors influencing the separation effect and the future study prospect.
Metal-organic frameworks(MOFs) are a new class of porous materials formed by the self-assembly of metal ions(or metal clusters) and organic ligands. Currently, the application of metal-organic frameworks in separation of light hydrocarbons including methane, acetylene, ethylene, ethane, propylene and propane has attracted tremendous interests. This article briefly reviews the latest development in this field, and discusses the factors influencing the separation effect and the future study prospect.
2017, 34(9): 1017-1023
doi: 10.11944/j.issn.1000-0518.2017.09.170144
Abstract:
Via stepwise assembly method, discrete mononuclear Ln(Ln=Tb/Sm/Yb) complexes were synthesized from 3-or 4-pyridyl modified tripodal ligands, which were then assembled into three dimensional Ln-M(M=Ag or Cd) metal-organic frameworks(MOFs) with different topologies through the linkage of pyridyl ends. The heteronuclear MOFs sustain a characteristic emission of Ln3+ coordination centers, but the energy levels of the ligands are lowered in the three-dimensional packing structures, which affects the energy transfer efficiency to lanthanide centers. As a result, a stronger near-infrared luminescence is obtained in 2-Yb-Ag compared with its mononuclear counterpart, and the decay lifetime increases from 4.3 μs to 6.7 μs. While 4-Tb-Cd simultaneously emits metal-centered and ligand-based emissions, in which the decay lifetime for Tb-centered emission shortens from 2.91 ms to 0.62 ms compared with the corresponding mononuclear complex.
Via stepwise assembly method, discrete mononuclear Ln(Ln=Tb/Sm/Yb) complexes were synthesized from 3-or 4-pyridyl modified tripodal ligands, which were then assembled into three dimensional Ln-M(M=Ag or Cd) metal-organic frameworks(MOFs) with different topologies through the linkage of pyridyl ends. The heteronuclear MOFs sustain a characteristic emission of Ln3+ coordination centers, but the energy levels of the ligands are lowered in the three-dimensional packing structures, which affects the energy transfer efficiency to lanthanide centers. As a result, a stronger near-infrared luminescence is obtained in 2-Yb-Ag compared with its mononuclear counterpart, and the decay lifetime increases from 4.3 μs to 6.7 μs. While 4-Tb-Cd simultaneously emits metal-centered and ligand-based emissions, in which the decay lifetime for Tb-centered emission shortens from 2.91 ms to 0.62 ms compared with the corresponding mononuclear complex.
2017, 34(9): 1035-1045
doi: 10.11944/j.issn.1000-0518.2017.09.170180
Abstract:
Metal-organic frameworks have promising potentials of for applications in the areas of fluorescence recognition. To explore more accurate identification of synthetic substancess, we synthesized two copper metal-organic frameworks(MOFs), {[Cu(PAIA)(H2O)]·2H2O}(1) and {[Cu3(PAIA)2(DMSO)(Pyridine)1.5]}(2)(H2PAIA=5-(propionyl-λ2-azanyl)isophthalic acid; DMSO=dimethyl sulphoxide), by the solvothermal reaction in the presence of H2PAIA under different solvents(H2O and DMSO/H2O). Synthetic investigations and structural analyses reveal that both MOFs show distinct frameworks with remarkable solvent-directed feature, although they are assembled from the same starting materials, i.e., Cu(NO3)2·3H2O with H2PAIA for complexes 1 and 2. The topological structures and fluorescent properties of the two coordination compounds show a significant difference. Complex 1 is a three-dimensional NbO-type topology, while the complex 2 is a two-dimensional sql-type topology. Complex 1 exhibits fluorescent recognition to both Pb2+ and Ag+ ions, while complex 2 exhibits fluorescent recognition of Pb2+ ion. The water contact angle for complex 1 is 85.06°, while the water contact angle for complex 2 is 52.71°.
Metal-organic frameworks have promising potentials of for applications in the areas of fluorescence recognition. To explore more accurate identification of synthetic substancess, we synthesized two copper metal-organic frameworks(MOFs), {[Cu(PAIA)(H2O)]·2H2O}(1) and {[Cu3(PAIA)2(DMSO)(Pyridine)1.5]}(2)(H2PAIA=5-(propionyl-λ2-azanyl)isophthalic acid; DMSO=dimethyl sulphoxide), by the solvothermal reaction in the presence of H2PAIA under different solvents(H2O and DMSO/H2O). Synthetic investigations and structural analyses reveal that both MOFs show distinct frameworks with remarkable solvent-directed feature, although they are assembled from the same starting materials, i.e., Cu(NO3)2·3H2O with H2PAIA for complexes 1 and 2. The topological structures and fluorescent properties of the two coordination compounds show a significant difference. Complex 1 is a three-dimensional NbO-type topology, while the complex 2 is a two-dimensional sql-type topology. Complex 1 exhibits fluorescent recognition to both Pb2+ and Ag+ ions, while complex 2 exhibits fluorescent recognition of Pb2+ ion. The water contact angle for complex 1 is 85.06°, while the water contact angle for complex 2 is 52.71°.
2017, 34(9): 1046-1051
doi: 10.11944/j.issn.1000-0518.2017.09.170188
Abstract:
Lanthanide coordination polymers have been widely investigated in fluorescent sensing owing to their characters in component, structure, and properties. However, the functional targeted construction of lanthanide coordination polymers is still a challenge. Herein, we report the construction, characterization, and properties investigation of a new Tb3+ coordination polymer, namely[Tb(TZI)(DMF)2(H2O)]·(H2O)(1)(H3TZI=5-(1H-tetrazol-5-yl)isophthalic acid and DMF=N, N-dimethylmethanamide). Utilizing the distinct affinities between Tb3+ ion and carboxylate/tetrazole groups, the construction of coordination polymer is well achieved, while the tetrazole group has been introduced into the framework of coordination polymer as sensing sites. As a result, complex 1 reveals ions dependent emissions enhancement owing to the coordination between the ions and the tetrazole sites, which could be utilized for the sensing of Zn2+ and Na+ ions. These results could be instructive for the fluorescent sensing function targeted construction of lanthanide coordination polymers.
Lanthanide coordination polymers have been widely investigated in fluorescent sensing owing to their characters in component, structure, and properties. However, the functional targeted construction of lanthanide coordination polymers is still a challenge. Herein, we report the construction, characterization, and properties investigation of a new Tb3+ coordination polymer, namely[Tb(TZI)(DMF)2(H2O)]·(H2O)(1)(H3TZI=5-(1H-tetrazol-5-yl)isophthalic acid and DMF=N, N-dimethylmethanamide). Utilizing the distinct affinities between Tb3+ ion and carboxylate/tetrazole groups, the construction of coordination polymer is well achieved, while the tetrazole group has been introduced into the framework of coordination polymer as sensing sites. As a result, complex 1 reveals ions dependent emissions enhancement owing to the coordination between the ions and the tetrazole sites, which could be utilized for the sensing of Zn2+ and Na+ ions. These results could be instructive for the fluorescent sensing function targeted construction of lanthanide coordination polymers.
2017, 34(9): 1052-1058
doi: 10.11944/j.issn.1000-0518.2017.09.170170
Abstract:
For luminescence sensing, Cu(Ⅰ)-based coordination complexes have unique advantages such as low cost and long luminescence lifetime. However, Cu(Ⅰ) coordination complexes are generally unstable in air, easily oxidized by oxygen, or quite difficult to form porous frameworks. Among various zeolitic zinc-imidazolate porous coordination polymers, RHO-[Zn(eim)2] (MAF-6, Heim=2-ethylimidazole) has received considerable interest due to its large pore size and superior hydrophobicity. In this paper, by virtue of the similar coordination behaviors of Cu(Ⅰ) and Zn(Ⅱ) ions, an isomorphic phosphorescent porous coordination polymer, Cu:MAF-6, was obtained through partial substituting Zn(Ⅱ) ions of MAF-6 with Cu(Ⅰ) ions. The phosphorescence of Cu:MAF-6 exhibits very high oxygen sensitivity(Ksv=28.09 kPa-1; limit of detection=0.36 Pa) in the low oxygen concentration environment( < 600 Pa).
For luminescence sensing, Cu(Ⅰ)-based coordination complexes have unique advantages such as low cost and long luminescence lifetime. However, Cu(Ⅰ) coordination complexes are generally unstable in air, easily oxidized by oxygen, or quite difficult to form porous frameworks. Among various zeolitic zinc-imidazolate porous coordination polymers, RHO-[Zn(eim)2] (MAF-6, Heim=2-ethylimidazole) has received considerable interest due to its large pore size and superior hydrophobicity. In this paper, by virtue of the similar coordination behaviors of Cu(Ⅰ) and Zn(Ⅱ) ions, an isomorphic phosphorescent porous coordination polymer, Cu:MAF-6, was obtained through partial substituting Zn(Ⅱ) ions of MAF-6 with Cu(Ⅰ) ions. The phosphorescence of Cu:MAF-6 exhibits very high oxygen sensitivity(Ksv=28.09 kPa-1; limit of detection=0.36 Pa) in the low oxygen concentration environment( < 600 Pa).
2017, 34(9): 1079-1085
doi: 10.11944/j.issn.1000-0518.2017.09.170191
Abstract:
It is a challenge to oxidize inert hydrocarbons with molecular oxygen, which can be easily realized by enzymes under mild conditions. Inspired by the catalytic mechanism of enzymes, we used the composite material CuPW11@HKUST-1, consisting of encapsulated Keggin-type polyoxometalate[CuPW11O39]5-(abbreviated as CuPW11) in the pore space of metal-organic framework HKUST-1, as a redox catalyst, and N-hydroxyphthalimide(NHPI) as a co-catalyst, for the biomimetic aerobic oxidation of arylalkanes under mild conditions. The biomimetic system exhibits enzyme-like features of high efficiency and high selectivity in the aerobic oxidation of arylalkanes by imitating the structural features, active sites and catalytic mechanism of enzymes, in which up to 99% yield and 17700 turnover number(TON) have been realized in the aerobic oxidation reaction. This work offers a feasible pathway for highly efficient aerobic oxidation of inert organic molecules under mild conditions.
It is a challenge to oxidize inert hydrocarbons with molecular oxygen, which can be easily realized by enzymes under mild conditions. Inspired by the catalytic mechanism of enzymes, we used the composite material CuPW11@HKUST-1, consisting of encapsulated Keggin-type polyoxometalate[CuPW11O39]5-(abbreviated as CuPW11) in the pore space of metal-organic framework HKUST-1, as a redox catalyst, and N-hydroxyphthalimide(NHPI) as a co-catalyst, for the biomimetic aerobic oxidation of arylalkanes under mild conditions. The biomimetic system exhibits enzyme-like features of high efficiency and high selectivity in the aerobic oxidation of arylalkanes by imitating the structural features, active sites and catalytic mechanism of enzymes, in which up to 99% yield and 17700 turnover number(TON) have been realized in the aerobic oxidation reaction. This work offers a feasible pathway for highly efficient aerobic oxidation of inert organic molecules under mild conditions.
2017, 34(9): 1086-1092
doi: 10.11944/j.issn.1000-0518.2017.09.170176
Abstract:
Two lanthanide cluster-based metal-organic frameworks of {[Gd7(OH)8(HOCH2COO)8(H2O)3]·Cl5·3H2O}n(Ln=Gd(1), Dy(2)) were obtained by solvothermal reaction. The magnetic studies indicate that compound 1 exhibits a large magnetocalotic effect(MCE) values of 44.4 J/(kg·K) at 2 K and △H=7 T and compound 2 displays obvious frequency dependence(Hdc=0) which suggests that compound 2 shows slow relaxation. In addition, the results of powder diffraction reveals that compounds 1 and 2 display very high chemical stability, which can be stable in acid/base solution of pH=1~14 and boiling water. These results indicate that the lanthanide cluster-based metal-organic frameworks have the potential application in the low-temperature refrigeration.
Two lanthanide cluster-based metal-organic frameworks of {[Gd7(OH)8(HOCH2COO)8(H2O)3]·Cl5·3H2O}n(Ln=Gd(1), Dy(2)) were obtained by solvothermal reaction. The magnetic studies indicate that compound 1 exhibits a large magnetocalotic effect(MCE) values of 44.4 J/(kg·K) at 2 K and △H=7 T and compound 2 displays obvious frequency dependence(Hdc=0) which suggests that compound 2 shows slow relaxation. In addition, the results of powder diffraction reveals that compounds 1 and 2 display very high chemical stability, which can be stable in acid/base solution of pH=1~14 and boiling water. These results indicate that the lanthanide cluster-based metal-organic frameworks have the potential application in the low-temperature refrigeration.
2017, 34(9): 1093-1098
doi: 10.11944/j.issn.1000-0518.2017.09.170060
Abstract:
By the hydrothermal reaction of Cd(NO3)2·4H2O with 2-(2-bromophenyl)-1H-imidazole-4, 5-dicarboxylic acid(o-BrPhH3IDC) and ammonium oxalate, a new wave-shaped chain complex {[Cd(o-BrPhH2IDC)2(H2O)]·H2O}n(1) was synthesized and characterized through elemental analysis, Fourier transform infrared spectrometer, thermogravimetric and single crystal X-ray diffraction analysis. The results show that complex 1 crystallizes in the orthorhombic space group Pbca. Excited by the wavelength of 316 nm, complex 1 shows the maximum fluorescence emission peak around 356 nm. Further experiments show that acetonitrile significantly increases the fluorescence intensity of complex 1, and methanol and ethanol may decrease the fluorescence intensity. If complex 1 is treated with pyridine, the fluorescence emission peak of complex 1 disappears, which indicates selective recognition for pyridine.
By the hydrothermal reaction of Cd(NO3)2·4H2O with 2-(2-bromophenyl)-1H-imidazole-4, 5-dicarboxylic acid(o-BrPhH3IDC) and ammonium oxalate, a new wave-shaped chain complex {[Cd(o-BrPhH2IDC)2(H2O)]·H2O}n(1) was synthesized and characterized through elemental analysis, Fourier transform infrared spectrometer, thermogravimetric and single crystal X-ray diffraction analysis. The results show that complex 1 crystallizes in the orthorhombic space group Pbca. Excited by the wavelength of 316 nm, complex 1 shows the maximum fluorescence emission peak around 356 nm. Further experiments show that acetonitrile significantly increases the fluorescence intensity of complex 1, and methanol and ethanol may decrease the fluorescence intensity. If complex 1 is treated with pyridine, the fluorescence emission peak of complex 1 disappears, which indicates selective recognition for pyridine.
2017, 34(9): 1024-1034
doi: 10.11944/j.issn.1000-0518.2017.09.170160
Abstract:
The solvothermal reaction of a viologen-functionalized aromatic dicarboxylate ligand 1-(3, 5-dicarboxybenzyl)-4, 4'-bipyridinium nitrate(H2L+NO3-) with Eu(Ⅲ) leads to the formation of a new metal-organic complex {[Eu(μ2-OH)(L)(HCO2)]·H2O}n(1), in which the formate anions come from the in situ decomposition of solvent dimethylformamide(DMF). Single-crystal X-ray analysis revealed that complex 1 has chirality and diaplays a two-dimensional layer structure. Complex 1 manifests fast photoresponsive and reversibile photochromic properties. It gives an eye-detectable color change from pale-yellow to dark green upon exposure to light, and the coloring/fading processes can repeat several cycles. The structural analysis demonstrated that the electrons transfer from carboxylate donors to viologen acceptor as well as the π....π interaction offers reasonable electron-transfer pathways for the photochromic process. Interestingly, the synthesized solid-state chiral crystalline material not only exhibits tunable luminescence in response to light, but also shows photoswitching nonlinear optical(NLO) activity, and the second-harmonic generation(SHG) efficiency is approximately 3.8 times that of potassium dihydrogen phosphate(KDP) in the same particle size. Moreover, surface photovoltage spectroscopy(SPS) of complex 1 has been investigated and the result indicates it exhibits interesting photovoltaic activity.
The solvothermal reaction of a viologen-functionalized aromatic dicarboxylate ligand 1-(3, 5-dicarboxybenzyl)-4, 4'-bipyridinium nitrate(H2L+NO3-) with Eu(Ⅲ) leads to the formation of a new metal-organic complex {[Eu(μ2-OH)(L)(HCO2)]·H2O}n(1), in which the formate anions come from the in situ decomposition of solvent dimethylformamide(DMF). Single-crystal X-ray analysis revealed that complex 1 has chirality and diaplays a two-dimensional layer structure. Complex 1 manifests fast photoresponsive and reversibile photochromic properties. It gives an eye-detectable color change from pale-yellow to dark green upon exposure to light, and the coloring/fading processes can repeat several cycles. The structural analysis demonstrated that the electrons transfer from carboxylate donors to viologen acceptor as well as the π....π interaction offers reasonable electron-transfer pathways for the photochromic process. Interestingly, the synthesized solid-state chiral crystalline material not only exhibits tunable luminescence in response to light, but also shows photoswitching nonlinear optical(NLO) activity, and the second-harmonic generation(SHG) efficiency is approximately 3.8 times that of potassium dihydrogen phosphate(KDP) in the same particle size. Moreover, surface photovoltage spectroscopy(SPS) of complex 1 has been investigated and the result indicates it exhibits interesting photovoltaic activity.
2017, 34(9): 1059-1065
doi: 10.11944/j.issn.1000-0518.2017.09.170189
Abstract:
Presented here are the solvothermal synthesis, structural characterization and fluorescent properties of a magnesium metal-organic framework(Mg-MOF), namely[Mg4(1, 4-NDC)4(DMA)2(CH3OH)2(H2O)2]·DMA·CH3OH(1, 1, 4-H2NDC=1, 4-naphthalene dicarboxylic acid, DMA=N, N'-Dimethylacetamide). Single-crystal X-ray diffraction studies revealed that compound 1 crystallized in the monoclinic space group P21/c(No.14) with a=2.06090(12) nm, b=2.21014(13) nm, c=1.50385(10) nm, β=111.399(3)°, V=6.3776(7) nm3, Z=4, Dc=1.403 g/cm3, F(000)=2824, R=0.0596 and wR=0.1225(I>2σ(I)). The structure of compound 1 features a three-dimensional(3D) network constructed from the 1, 4-NDC ligands as bridging linkers and binuclear magnesium clusters as the secondary building units, with cages occupied by different solvent molecules of DMA and CH3OH. Notably, fluorescence studies revealed that compound 1 demonstrated sensitive sensing towards carbon disulfide(CS2); remarkably, the fluorescence intensity of compound 1 could be almost completely quenched at the low concentration of 0.4%(volume fraction) of CS2. Thermal stability was investigated by thermogravimetric analysis which indicated that compound 1 could be stable up to 140℃.
Presented here are the solvothermal synthesis, structural characterization and fluorescent properties of a magnesium metal-organic framework(Mg-MOF), namely[Mg4(1, 4-NDC)4(DMA)2(CH3OH)2(H2O)2]·DMA·CH3OH(1, 1, 4-H2NDC=1, 4-naphthalene dicarboxylic acid, DMA=N, N'-Dimethylacetamide). Single-crystal X-ray diffraction studies revealed that compound 1 crystallized in the monoclinic space group P21/c(No.14) with a=2.06090(12) nm, b=2.21014(13) nm, c=1.50385(10) nm, β=111.399(3)°, V=6.3776(7) nm3, Z=4, Dc=1.403 g/cm3, F(000)=2824, R=0.0596 and wR=0.1225(I>2σ(I)). The structure of compound 1 features a three-dimensional(3D) network constructed from the 1, 4-NDC ligands as bridging linkers and binuclear magnesium clusters as the secondary building units, with cages occupied by different solvent molecules of DMA and CH3OH. Notably, fluorescence studies revealed that compound 1 demonstrated sensitive sensing towards carbon disulfide(CS2); remarkably, the fluorescence intensity of compound 1 could be almost completely quenched at the low concentration of 0.4%(volume fraction) of CS2. Thermal stability was investigated by thermogravimetric analysis which indicated that compound 1 could be stable up to 140℃.
2017, 34(9): 1066-1071
doi: 10.11944/j.issn.1000-0518.2017.09.170179
Abstract:
Adsorption of dyes has received wide attention due to its threat to human health and environment. In this work, a new oxalamide-functionalized anionic metal-organic framework {[(CH3)2NH2]2(CdL)}·x(Solvent)(1) has been successfully synthesized by virtue of a tetratopic ligand of 5, 5'-[oxalylbis(azanediyl)]diisophthalic acid (H4L). Single crystal X-ray diffraction reveals that compound 1 exhibits a 2-fold interpenetrated 3D framework and (3, 3, 4)-connected topological network with a new point(Schläfli) symbol of {83}2{86}. Interestingly, it displays not only selective adsorption capacity toward methylene blue(MB) over methyl orange(MO), but also the photoluminescence emission at visible region.
Adsorption of dyes has received wide attention due to its threat to human health and environment. In this work, a new oxalamide-functionalized anionic metal-organic framework {[(CH3)2NH2]2(CdL)}·x(Solvent)(1) has been successfully synthesized by virtue of a tetratopic ligand of 5, 5'-[oxalylbis(azanediyl)]diisophthalic acid (H4L). Single crystal X-ray diffraction reveals that compound 1 exhibits a 2-fold interpenetrated 3D framework and (3, 3, 4)-connected topological network with a new point(Schläfli) symbol of {83}2{86}. Interestingly, it displays not only selective adsorption capacity toward methylene blue(MB) over methyl orange(MO), but also the photoluminescence emission at visible region.
2017, 34(9): 1072-1078
doi: 10.11944/j.issn.1000-0518.2017.09.170183
Abstract:
Zeolitic metal-organic frameworks(MOFs) with high porosity, controlled pore size, regular pore shape, high thermal and chemical stability have been extensively studied and display potential applications in the field of rapid accumulation of iodine. Here, through simulating the structure of zeolite, two tetrahedral tetrazolate frameworks(TTF-8 and TTF-9) were successfully assembled via using thiophene-2, 5-dicarboxylate and 4, 4'-oxybisbenzoic acid as an auxiliary ligand, respectively. The results of single-crystal X-ray diffraction measurement show that TTF-8 crystallizes in a tetragonal space group of P42mc, while TTF-9 exhibits a monoclinic space group of P21/c. Remarkably, although TTF-8 and TTF-9 exhibit the same BCT topology, their frameworks and pore structures are entirely different. Two TTFs materials display outstanding performance on rapidly enriching iodine.
Zeolitic metal-organic frameworks(MOFs) with high porosity, controlled pore size, regular pore shape, high thermal and chemical stability have been extensively studied and display potential applications in the field of rapid accumulation of iodine. Here, through simulating the structure of zeolite, two tetrahedral tetrazolate frameworks(TTF-8 and TTF-9) were successfully assembled via using thiophene-2, 5-dicarboxylate and 4, 4'-oxybisbenzoic acid as an auxiliary ligand, respectively. The results of single-crystal X-ray diffraction measurement show that TTF-8 crystallizes in a tetragonal space group of P42mc, while TTF-9 exhibits a monoclinic space group of P21/c. Remarkably, although TTF-8 and TTF-9 exhibit the same BCT topology, their frameworks and pore structures are entirely different. Two TTFs materials display outstanding performance on rapidly enriching iodine.
