Two new 3D,Zn(Ⅱ)–organic frameworks,[{Zn(BINDI)_(0.5)(bpa)_(0.5)(H_(2)O)}·4H_(2)O]_(n)(MOF1)and[{Zn(BINDI)_(0.5)(bpe)}·3H_(2)O]_(n)(MOF2)(where H_(4)BINDI=N,N’-bis(5-isophthalic acid)naphthalenediimide,bp...Two new 3D,Zn(Ⅱ)–organic frameworks,[{Zn(BINDI)_(0.5)(bpa)_(0.5)(H_(2)O)}·4H_(2)O]_(n)(MOF1)and[{Zn(BINDI)_(0.5)(bpe)}·3H_(2)O]_(n)(MOF2)(where H_(4)BINDI=N,N’-bis(5-isophthalic acid)naphthalenediimide,bpa=1,2-bis(4-pyridyl)ethane and bpe=1,2-bis(4-pyridyl)ethylene),have been successfully synthesized by room temperature self-assembly and structurally characterized.Both MOF1 and 2 show 2-fold interpenetrated 3D framework structures with 1D channels of dimensions 4.4×9.5 and 4.6×2.5Å^(2) respectively.Gas adsorption studies of the MOFs revealed selective and higher CO_(2) uptake properties of MOF1 over 2 owing to the presence of a polar pore surface and an optimum pore size of 1 for CO_(2) gas molecules.Furthermore,the high water stability and luminescence properties of MOF1 and 2 were exploited for sensing of nitroaromatic pollutants in water.Consequently,both the MOFs exhibit highly selective aqueous-phase sensing of 2,4,6-trinitrophenol(TNP)through a luminescence quenching mechanism.Furthermore,MOF1 exhibits a relatively higher efficiency of TNP detection(LOD=0.6 ppm,K_(sv)=4.9×10^(4) M^(−1))compared to 2(LOD=1.5 ppm,K_(sv)=1.29×10^(4) M^(−1))due to higher resonance energy transfer between MOF1 and TNP owing to their better spectral overlap.Herein,the influence of N,N’-donor spacers on the structure,selective gas adsorption and the sensing properties of two new Zn(Ⅱ)MOFs has been demonstrated.展开更多
In most instances,the incursion of functional groups on the inner surface of microporous MOFs could undoubtedly result in a significant improvement of their desirable performances,inspired by which one amino-functiona...In most instances,the incursion of functional groups on the inner surface of microporous MOFs could undoubtedly result in a significant improvement of their desirable performances,inspired by which one amino-functionalized ligand 2,6-di(3,5-dicarboxylphenyl)-4-aminobenzoic acid(H_(5)DDAC)was designed and synthesized.By employing H_(5)DDAC as the organic linker,the exquisite combination of dinuclear[Eu_(2)(CO_(2))_(9)]and[Eu_(2)(CO_(2))_(6)(H_(2)O)_(2)]generated one highly robust microporous framework of{(Me_(2)NH_(2))_(4)[Eu_(4)(DDAC)_(3)(HCO_(2))(OH_(2))_(2)]·8DMF·9H_(2)O}n(NUC-41),which was characterized by hierarchical channels and cage-like voids.Owing to the Lewis acid-base synergistic effect including open metal sites,free oxygen atoms and amino groups,NUC-41 with the aid of cocatalyst n-Bu_(4)NBr exhibited extremely high catalytic activity for the cycloaddition reactions of alkyl epoxides and CO_(2)under mild solvent-free conditions,especially for epoxides with a smaller size.Furthermore,fluorescence experiments confirmed that the amino-functionalized skeleton of NUC-41 could effectively sense 2,4,6-trinitrophenol in aqueous solution over other nitro analytes including TNP,2,4-DNP,4-NP,2,4-DNT,TNT,1,4-DNB,4-NT and NB with KSV and the limit of detection being 8.6×10_(4)M^(−1)and 3.5×10^(−6)M,respectively.Therefore,these results indicate that amino functionalization is an effective strategy to improve and expand the application performance of MOFs,which is critically related to the sustainable development of MOF research in this day and age.展开更多
A novel energetic coordination compound, rubidium 3,5-dihydroxy-2,4,6-trinitrophenolate ([Rb(DHTNP)]n), has been synthesized by reaction of trinitrophloroglucinol with Rb2CO3 in aqueous solution. Its crystal structure...A novel energetic coordination compound, rubidium 3,5-dihydroxy-2,4,6-trinitrophenolate ([Rb(DHTNP)]n), has been synthesized by reaction of trinitrophloroglucinol with Rb2CO3 in aqueous solution. Its crystal structure has been determined. The crystal belongs to monoclinic system with space group C2 / c. In the crystal the Rb cation is coordinated to ten oxygen atoms from seven different DHTNP- anions to form an irregular polyhedron. Two independent molecule geometry structures are found for DHTNP- anion in the complex, which differ in benzene ring and their pattern of intramolecular hydrogen bonds. The DHTNP- anion chains are interlaced with rubidium atoms as knots, and a three-dimensional infinite net structure is formed via coordination and hydrogen bonding. The hydrogen bond and cation-anion interactions are the predominant driving forces in the crystal packing. The thermal property of title complex was studied by using DSC and TG-DTG techniques. CCDC: 290623.展开更多
在p H 7.4的0.20 mol/L Na H2PO4-Na2HPO4缓冲溶液中,阿魏酸与2,4,6-三硝基苯酚混合后,使得阿魏酸在激发波长355 nm、发射波长455 nm条件下荧光被猝灭,其相对荧光强度在一定范围内与2,4,6-三硝基苯酚的浓度呈线性关系,从而建立了荧光猝...在p H 7.4的0.20 mol/L Na H2PO4-Na2HPO4缓冲溶液中,阿魏酸与2,4,6-三硝基苯酚混合后,使得阿魏酸在激发波长355 nm、发射波长455 nm条件下荧光被猝灭,其相对荧光强度在一定范围内与2,4,6-三硝基苯酚的浓度呈线性关系,从而建立了荧光猝灭法测定2,4,6-三硝基苯酚的新方法。该方法的线性范围为1.00-100.00μmol/L,检出限为0.22μmol/L。本方法已用于环境水样中2,4,6-三硝基苯酚的检测,回收率为98.00%-102.47%。展开更多
文摘Two new 3D,Zn(Ⅱ)–organic frameworks,[{Zn(BINDI)_(0.5)(bpa)_(0.5)(H_(2)O)}·4H_(2)O]_(n)(MOF1)and[{Zn(BINDI)_(0.5)(bpe)}·3H_(2)O]_(n)(MOF2)(where H_(4)BINDI=N,N’-bis(5-isophthalic acid)naphthalenediimide,bpa=1,2-bis(4-pyridyl)ethane and bpe=1,2-bis(4-pyridyl)ethylene),have been successfully synthesized by room temperature self-assembly and structurally characterized.Both MOF1 and 2 show 2-fold interpenetrated 3D framework structures with 1D channels of dimensions 4.4×9.5 and 4.6×2.5Å^(2) respectively.Gas adsorption studies of the MOFs revealed selective and higher CO_(2) uptake properties of MOF1 over 2 owing to the presence of a polar pore surface and an optimum pore size of 1 for CO_(2) gas molecules.Furthermore,the high water stability and luminescence properties of MOF1 and 2 were exploited for sensing of nitroaromatic pollutants in water.Consequently,both the MOFs exhibit highly selective aqueous-phase sensing of 2,4,6-trinitrophenol(TNP)through a luminescence quenching mechanism.Furthermore,MOF1 exhibits a relatively higher efficiency of TNP detection(LOD=0.6 ppm,K_(sv)=4.9×10^(4) M^(−1))compared to 2(LOD=1.5 ppm,K_(sv)=1.29×10^(4) M^(−1))due to higher resonance energy transfer between MOF1 and TNP owing to their better spectral overlap.Herein,the influence of N,N’-donor spacers on the structure,selective gas adsorption and the sensing properties of two new Zn(Ⅱ)MOFs has been demonstrated.
基金supported by the Natural Science Foundation of China(21101097)the Opening Foundation of Key Laboratory of Laser&Infrared System of Shandong University(2019-LISKFJJ-005).
文摘In most instances,the incursion of functional groups on the inner surface of microporous MOFs could undoubtedly result in a significant improvement of their desirable performances,inspired by which one amino-functionalized ligand 2,6-di(3,5-dicarboxylphenyl)-4-aminobenzoic acid(H_(5)DDAC)was designed and synthesized.By employing H_(5)DDAC as the organic linker,the exquisite combination of dinuclear[Eu_(2)(CO_(2))_(9)]and[Eu_(2)(CO_(2))_(6)(H_(2)O)_(2)]generated one highly robust microporous framework of{(Me_(2)NH_(2))_(4)[Eu_(4)(DDAC)_(3)(HCO_(2))(OH_(2))_(2)]·8DMF·9H_(2)O}n(NUC-41),which was characterized by hierarchical channels and cage-like voids.Owing to the Lewis acid-base synergistic effect including open metal sites,free oxygen atoms and amino groups,NUC-41 with the aid of cocatalyst n-Bu_(4)NBr exhibited extremely high catalytic activity for the cycloaddition reactions of alkyl epoxides and CO_(2)under mild solvent-free conditions,especially for epoxides with a smaller size.Furthermore,fluorescence experiments confirmed that the amino-functionalized skeleton of NUC-41 could effectively sense 2,4,6-trinitrophenol in aqueous solution over other nitro analytes including TNP,2,4-DNP,4-NP,2,4-DNT,TNT,1,4-DNB,4-NT and NB with KSV and the limit of detection being 8.6×10_(4)M^(−1)and 3.5×10^(−6)M,respectively.Therefore,these results indicate that amino functionalization is an effective strategy to improve and expand the application performance of MOFs,which is critically related to the sustainable development of MOF research in this day and age.
文摘A novel energetic coordination compound, rubidium 3,5-dihydroxy-2,4,6-trinitrophenolate ([Rb(DHTNP)]n), has been synthesized by reaction of trinitrophloroglucinol with Rb2CO3 in aqueous solution. Its crystal structure has been determined. The crystal belongs to monoclinic system with space group C2 / c. In the crystal the Rb cation is coordinated to ten oxygen atoms from seven different DHTNP- anions to form an irregular polyhedron. Two independent molecule geometry structures are found for DHTNP- anion in the complex, which differ in benzene ring and their pattern of intramolecular hydrogen bonds. The DHTNP- anion chains are interlaced with rubidium atoms as knots, and a three-dimensional infinite net structure is formed via coordination and hydrogen bonding. The hydrogen bond and cation-anion interactions are the predominant driving forces in the crystal packing. The thermal property of title complex was studied by using DSC and TG-DTG techniques. CCDC: 290623.
文摘在p H 7.4的0.20 mol/L Na H2PO4-Na2HPO4缓冲溶液中,阿魏酸与2,4,6-三硝基苯酚混合后,使得阿魏酸在激发波长355 nm、发射波长455 nm条件下荧光被猝灭,其相对荧光强度在一定范围内与2,4,6-三硝基苯酚的浓度呈线性关系,从而建立了荧光猝灭法测定2,4,6-三硝基苯酚的新方法。该方法的线性范围为1.00-100.00μmol/L,检出限为0.22μmol/L。本方法已用于环境水样中2,4,6-三硝基苯酚的检测,回收率为98.00%-102.47%。
