Complex multiscale assemblies of metal-organic frameworks are essential in the construction of largescale optical platforms but often restricted by their bulk nature and conventional techniques.The integration of nano...Complex multiscale assemblies of metal-organic frameworks are essential in the construction of largescale optical platforms but often restricted by their bulk nature and conventional techniques.The integration of nanomaterials and 3D printing technologies allows the fabrication of multiscale functional architectures.Our study reports a unique method of controlled 3D assembly purely relying on the post-printing treatment of printed constructs.By immersing a 3D-printed patterned construct consisting of organic ligand in a solution of lanthanide ions,in situ growth of lanthanide metal-organic frameworks(LnMOFs)can rapidly occur,resulting in macroscopic assemblies and tunable fluorescence properties.This phenomenon,caused by coordination and chelation of lanthanide ions,also renders a sub-millimeter resolution and high shape fidelity.As a proof of concept,a type of 3D assembled LnMOFsbased optical sensing platform has demonstrated the feasibility in response to small molecules such as acetone.It is anticipated that the facile printing and design approach developed in this work can be applied to fabricate bespoke multiscale architectures of functional materials with controlled assembly,bringing a realistic and economic prospect.展开更多
Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=P...Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=Pamoic acid, DMA=dimethylacetamide, DMF=N,N-dimethylformamide）, have been synthesized by the reaction of Ln（NO3）a-6H20 with pamoic acid through layer diffusion method. These complexes were characterized by single crystal X-ray diffraction, infrared spectroscopy （IR）, thermogravimetric analysis （TGA）, fluorescence and magnetic measurements. Solvents and lanthanide atoms in the reaction play an important role in controlling different structures. Type I demonstrated 1-D linear chain structure connected by Ln atoms and PA ligands. Type II exhibited non-interpenetrating 3-D 6-connected 43612 nets based on binuclear [Ln2（CO2）6（DMF）4] cores. Magnetic properties of complexes 1-4 were investigated in details. Complex 1 shows significant magnetocaloric effect with -△Sm=20.37 J kg^-1 K^-1 at 3.0 K and 7 T. Complex 2 exhibits slow relaxation of the magnetization. Complexes 3-6 exhibit both ligand- and metal-centered fluorescent properties. Complex 6 demonstrates fluorescent sensing of DMF and Cu^2＋ ion.展开更多
Due to the potential risk of antibiotics to the environment,the development of inexpensive,simple,and reliable antibiotic detection methods is significant but also faces challenges.In this work,several lanthanide-orga...Due to the potential risk of antibiotics to the environment,the development of inexpensive,simple,and reliable antibiotic detection methods is significant but also faces challenges.In this work,several lanthanide-organic frameworks(LOFs),constructed from lanthanide ions(Eu3+and/or Tb3+)and 1,3,5-benzene-tricarboxylic acid(BTC),were synthesized by solvothermal method.LOF-S3 with comparable emission peaks of 5D4→7F5(Tb3+,545 nm)and 5D0→7F2(Eu3+,618 nm)was selected as a luminescent sensor.In this system,the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb3+to Eu3+occurs.LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios.Therefore,a two-dimensional decoded map of antibiotics was established.The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible.As a typical analyte,the response mechanism of nalidixic acid(NA)was investigated in detail.The competition of NA and BTC for UV light absorption,as well as the binding propensity of NA and Tb,affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer,resulting in the change of fluorescence intensity ratio.The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles.Furthermore,the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability,which is a promising portable sensor for practical applications.展开更多
Two isomorphic 3D lanthanide metal-organic frameworks,{[Tb(L)0.5(OX)0.5(H2 O)2DMF]·DMF}n(1)and{[Dy(L)0.5(OX)0.5(H2 O)2 DMF]·DMF}n(2),have been prepared under solvothermal conditions based on l,4-bis(3,5-dica...Two isomorphic 3D lanthanide metal-organic frameworks,{[Tb(L)0.5(OX)0.5(H2 O)2DMF]·DMF}n(1)and{[Dy(L)0.5(OX)0.5(H2 O)2 DMF]·DMF}n(2),have been prepared under solvothermal conditions based on l,4-bis(3,5-dicarboxylicpyrazol-1-ylmethyl)benzene(H4 L),oxalis acid(H2 OX)and lanthanide ions.Compound 1 crystallizes in monoclinic system,space group P21/c with a=9.418(15),b=15.23(2),c=14.47(2)?,β=100.07(3)°,V=2044(5)?3,Z=4,Mr=590.3 g/mol,Dc=1.919 g/cm^3,μ=3.524 mm-1,F(000)=1168,R=0.0893 and wR=0.1902 for 3486 observed reflections(I>2σ(I)).In compound 1,the central terbium(Ⅲ)ions are coordinated with eight atoms,and two neighboring terbium(Ⅲ)ions are linked together by one bridging oxalic acid group to give rise to a[Tb2(OX)(L)4]unit.Each[Tb2(OX)(L)4]unit connects to the surrounding six identical ones by the oxygen atoms bridging to lead to a 3D framework.Compound 1 exhibits strong luminescent emissions at the solid state owing to the antenna effect of the ligand.展开更多
Thermal sensing and imaging in the physiological temperature range are of great importance for studying physiological processes and treating diseases. Metal-organic frameworks(MOFs) exhibit great promise for developin...Thermal sensing and imaging in the physiological temperature range are of great importance for studying physiological processes and treating diseases. Metal-organic frameworks(MOFs) exhibit great promise for developing luminescent thermometers due to their remarkable structural diversities and tunable luminescence properties. Here, we synthesized a series of luminescent mixed-lanthanide MOFs,EuTbBPT(x = 0.019, 0.058, 0.106; H3 BPT = biphenyl-3,4’,5-tricarboxylate acid) and adopted powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA) and Fourier transform infrared(FT-IR) to characterize the resulting products. The temperature-dependent photoluminescence emission spectra were recorded to investigate their potential applications in physiological temperature readout. It is found that the intensity ratio of Tbto Euis linearly correlated with temperature and the relative sensitivity is higher than 1.5%/℃ over the entire physiological temperature range. Furthermore,the temperaturedependent luminescence color emission allows for visual colorimetric temperature measurements.Luminescence lifetime testing and triplet energy level measurement were further conducted to study the mechanism.展开更多
The two three-dimensional oxo-bfidged lanthanides {[Ln2（C4H2O4）3（H20）4]· 3H2O}3, with Ln=Ho3＋ （1）; Gd3＋ （2）, are isomorphous. They have layer-type structures built up from non-centrosymrnetric dinuclear...The two three-dimensional oxo-bfidged lanthanides {[Ln2（C4H2O4）3（H20）4]· 3H2O}3, with Ln=Ho3＋ （1）; Gd3＋ （2）, are isomorphous. They have layer-type structures built up from non-centrosymrnetric dinuclear unit Ln2O12（H2O）4, beside three lattice H20 molecules stabilizing the 3D open-frmnework. The building entities are linked through one classical syn-anti g2-carboxylato-K1O：K^1O＇ bridge. Within the bi-polyhedra, two double μ2-O＇; K2O,O＇ bridges and a syn-syn classical one, support the magnetic measurements carried out on holmium compound indicating relatively weak anti-ferromagnetic interactions. The compari- son with magnetic studies on the almost similar reported Gd（III） compound, suggested that concomitant antiferromagnetic and ferro- magnetic properties could not be excluded. The two distinct thermal behaviors evidenced the higher metal-water bond strength with the smaller cation, and revealed the great supramolecular effects generated by hydrogen-bonding patterns.展开更多
A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemen...A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows： orthorhombic system, space group P212121 with a = 13.8287（7）, b = 14.0715（7）, c = 25.7403（12） A^°, V = 5008.8（4） A^°3, Mr = 1333.08, Z = 4, F（000） = 2644, Dc = 1.768 g/cm^3, μ（MoKα） = 3.189 mm^-1, the final R = 0.0351 and wR = 0.0814 （I 〉 2σ（I））. Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism （VCD） spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.展开更多
基金the financial support from the National Science Foundation of China(NSFC)(No.51733003).
文摘Complex multiscale assemblies of metal-organic frameworks are essential in the construction of largescale optical platforms but often restricted by their bulk nature and conventional techniques.The integration of nanomaterials and 3D printing technologies allows the fabrication of multiscale functional architectures.Our study reports a unique method of controlled 3D assembly purely relying on the post-printing treatment of printed constructs.By immersing a 3D-printed patterned construct consisting of organic ligand in a solution of lanthanide ions,in situ growth of lanthanide metal-organic frameworks(LnMOFs)can rapidly occur,resulting in macroscopic assemblies and tunable fluorescence properties.This phenomenon,caused by coordination and chelation of lanthanide ions,also renders a sub-millimeter resolution and high shape fidelity.As a proof of concept,a type of 3D assembled LnMOFsbased optical sensing platform has demonstrated the feasibility in response to small molecules such as acetone.It is anticipated that the facile printing and design approach developed in this work can be applied to fabricate bespoke multiscale architectures of functional materials with controlled assembly,bringing a realistic and economic prospect.
基金supported by the National Natural Science Foundation of China(21571092,21403102)the Natural Science Foundation of Shandong Province(ZR2012BQ023)the University Scientific Research Development Plan of the Education Department of Shandong Province(J14LC10)
文摘Two types of lanthanide coordination polymers, namely, [Ln（PA）（NO3）（DMA）3]n （Ln=Gd （1）, Dy （2）, Eu （3）, Tb （4）） （type I）, and {[Ln2（PA）3（DMF）4]＇2DMF} （Ln=Eu （5）, Tb （6）） （type II） （PA=Pamoic acid, DMA=dimethylacetamide, DMF=N,N-dimethylformamide）, have been synthesized by the reaction of Ln（NO3）a-6H20 with pamoic acid through layer diffusion method. These complexes were characterized by single crystal X-ray diffraction, infrared spectroscopy （IR）, thermogravimetric analysis （TGA）, fluorescence and magnetic measurements. Solvents and lanthanide atoms in the reaction play an important role in controlling different structures. Type I demonstrated 1-D linear chain structure connected by Ln atoms and PA ligands. Type II exhibited non-interpenetrating 3-D 6-connected 43612 nets based on binuclear [Ln2（CO2）6（DMF）4] cores. Magnetic properties of complexes 1-4 were investigated in details. Complex 1 shows significant magnetocaloric effect with -△Sm=20.37 J kg^-1 K^-1 at 3.0 K and 7 T. Complex 2 exhibits slow relaxation of the magnetization. Complexes 3-6 exhibit both ligand- and metal-centered fluorescent properties. Complex 6 demonstrates fluorescent sensing of DMF and Cu^2＋ ion.
基金supported by the 2020 Young Teacher Education Project of Fujian Provincial Department of Education(No.JAT200008)the 2017 Major Science and Technology Program for Water Pollution Control and Treatment(No.2017ZX07202).
文摘Due to the potential risk of antibiotics to the environment,the development of inexpensive,simple,and reliable antibiotic detection methods is significant but also faces challenges.In this work,several lanthanide-organic frameworks(LOFs),constructed from lanthanide ions(Eu3+and/or Tb3+)and 1,3,5-benzene-tricarboxylic acid(BTC),were synthesized by solvothermal method.LOF-S3 with comparable emission peaks of 5D4→7F5(Tb3+,545 nm)and 5D0→7F2(Eu3+,618 nm)was selected as a luminescent sensor.In this system,the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb3+to Eu3+occurs.LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios.Therefore,a two-dimensional decoded map of antibiotics was established.The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible.As a typical analyte,the response mechanism of nalidixic acid(NA)was investigated in detail.The competition of NA and BTC for UV light absorption,as well as the binding propensity of NA and Tb,affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer,resulting in the change of fluorescence intensity ratio.The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles.Furthermore,the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability,which is a promising portable sensor for practical applications.
基金supported by the National Natural Science Foundation of China(21701116,21671139 and 21501122)the Doctor Scientific Research Foundation of Liaoning Province(201601201 and 201601193)Program for Liaoning Innovative Research Team in University(No.2018012)。
文摘Two isomorphic 3D lanthanide metal-organic frameworks,{[Tb(L)0.5(OX)0.5(H2 O)2DMF]·DMF}n(1)and{[Dy(L)0.5(OX)0.5(H2 O)2 DMF]·DMF}n(2),have been prepared under solvothermal conditions based on l,4-bis(3,5-dicarboxylicpyrazol-1-ylmethyl)benzene(H4 L),oxalis acid(H2 OX)and lanthanide ions.Compound 1 crystallizes in monoclinic system,space group P21/c with a=9.418(15),b=15.23(2),c=14.47(2)?,β=100.07(3)°,V=2044(5)?3,Z=4,Mr=590.3 g/mol,Dc=1.919 g/cm^3,μ=3.524 mm-1,F(000)=1168,R=0.0893 and wR=0.1902 for 3486 observed reflections(I>2σ(I)).In compound 1,the central terbium(Ⅲ)ions are coordinated with eight atoms,and two neighboring terbium(Ⅲ)ions are linked together by one bridging oxalic acid group to give rise to a[Tb2(OX)(L)4]unit.Each[Tb2(OX)(L)4]unit connects to the surrounding six identical ones by the oxygen atoms bridging to lead to a 3D framework.Compound 1 exhibits strong luminescent emissions at the solid state owing to the antenna effect of the ligand.
基金supported by the National Natural Science Foundation of China(51432001,51472217,51632008,U1609219)
文摘Thermal sensing and imaging in the physiological temperature range are of great importance for studying physiological processes and treating diseases. Metal-organic frameworks(MOFs) exhibit great promise for developing luminescent thermometers due to their remarkable structural diversities and tunable luminescence properties. Here, we synthesized a series of luminescent mixed-lanthanide MOFs,EuTbBPT(x = 0.019, 0.058, 0.106; H3 BPT = biphenyl-3,4’,5-tricarboxylate acid) and adopted powder X-ray diffraction(PXRD), thermogravimetric analysis(TGA) and Fourier transform infrared(FT-IR) to characterize the resulting products. The temperature-dependent photoluminescence emission spectra were recorded to investigate their potential applications in physiological temperature readout. It is found that the intensity ratio of Tbto Euis linearly correlated with temperature and the relative sensitivity is higher than 1.5%/℃ over the entire physiological temperature range. Furthermore,the temperaturedependent luminescence color emission allows for visual colorimetric temperature measurements.Luminescence lifetime testing and triplet energy level measurement were further conducted to study the mechanism.
基金Project supported by MESRS-Algeria and MDU-France(project CMEP-Programme Tassili)
文摘The two three-dimensional oxo-bfidged lanthanides {[Ln2（C4H2O4）3（H20）4]· 3H2O}3, with Ln=Ho3＋ （1）; Gd3＋ （2）, are isomorphous. They have layer-type structures built up from non-centrosymrnetric dinuclear unit Ln2O12（H2O）4, beside three lattice H20 molecules stabilizing the 3D open-frmnework. The building entities are linked through one classical syn-anti g2-carboxylato-K1O：K^1O＇ bridge. Within the bi-polyhedra, two double μ2-O＇; K2O,O＇ bridges and a syn-syn classical one, support the magnetic measurements carried out on holmium compound indicating relatively weak anti-ferromagnetic interactions. The compari- son with magnetic studies on the almost similar reported Gd（III） compound, suggested that concomitant antiferromagnetic and ferro- magnetic properties could not be excluded. The two distinct thermal behaviors evidenced the higher metal-water bond strength with the smaller cation, and revealed the great supramolecular effects generated by hydrogen-bonding patterns.
基金supported by the Zhejiang Sci-Tech University Shengzhou Innovation Research Institute(SYY2.023C000005)the National Natural Science Foundation of China(51803184)。
基金supported by National Natural Science Foundation of China(21401147)Basic Research Program of Natural Science from Shaanxi Provincial Government(2015JQ2032)+2 种基金Scientific Research Program from Education Department of Shaanxi Provincial Government(2013JK0654)Opening Foundation from State Key Laboratory of Coordination Chemistry in Nanjing University(201219)the Program for Distinguished Young Scholars of Xi’an Polytechnic University(201403)
文摘A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows： orthorhombic system, space group P212121 with a = 13.8287（7）, b = 14.0715（7）, c = 25.7403（12） A^°, V = 5008.8（4） A^°3, Mr = 1333.08, Z = 4, F（000） = 2644, Dc = 1.768 g/cm^3, μ（MoKα） = 3.189 mm^-1, the final R = 0.0351 and wR = 0.0814 （I 〉 2σ（I））. Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism （VCD） spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.
