The synthesis,characterisation and capability to selectively detect vapours of volatile organic compounds(VOCs)and nitroaromatic explosives of a new family of 2-dimensional rare earth(RE)MOFs based on a hexanuclear(RE...The synthesis,characterisation and capability to selectively detect vapours of volatile organic compounds(VOCs)and nitroaromatic explosives of a new family of 2-dimensional rare earth(RE)MOFs based on a hexanuclear(RE^(3+))6 secondary building unit(SBU)is reported.The reaction of RE(NO_(3))_(3)with 4,4’-sulfonyldibenzoic acid(H_(2)SDBA)in the presence of 2-fluorobenzoic acid(HFBA)in DMF/MeOH at 100℃afforded compound[RE6(μ_(3)-OH/F)_(8)(SDBA)4(NO_(3))2(H_(2)O)_(6)]_(n)(UCY-15(RE);RE:Y,Eu,Gd,Tb,Dy,Ho,Er).展开更多
A new Cu^(2+)complex that was isolated from the initial use of 5-((pyridin-4-ylmethylene)amino)isophthalic acid(PEIPH_(2))in 3d metal–organic framework(MOF)chemistry is reported.Complex{[Cu_(3)(PEIP)_(2)(5-NH_(2)-mBD...A new Cu^(2+)complex that was isolated from the initial use of 5-((pyridin-4-ylmethylene)amino)isophthalic acid(PEIPH_(2))in 3d metal–organic framework(MOF)chemistry is reported.Complex{[Cu_(3)(PEIP)_(2)(5-NH_(2)-mBDC)(DMF)]·7DMF}_(∞) denoted as Cu-PEIP·7DMF was isolated from the reaction of Cu(NO_(3))_(2)·2.5H_(2)O with PEIPH_(2) in N,N-dimethylformamide(DMF)at 100℃ and contains both the PEIP2−ligand and its 5-NH_(2)-mBDC2−fragment.After the structure and properties of Cu-PEIP were known an analogous complex was prepared by a rational synthetic method that involved the reaction of Cu(NO_(3))_(2)·2.5H_(2)O,5-((pyridin-4-ylmethyl)amino)isophthalic acid(PIPH_(2)–the reduced analogue of PEIPH_(2))and 5-NH_(2)-mBDCH_(2) in DMF at 100℃.Cu-PEIP comprises two paddle-wheel[Cu_(2)(COO)_(4)]units and exhibits a 3Dframework with a unique trinodal underlying network and point symbol(4.5^(2))_(4)(4^(2)·5^(4)·6^(4)·8^(3)·9^(2))_(2)(5^(2)·8^(4)).This network consists of pillared kgm-a layers containing a hexagonal shaped cavity with a relatively large diameter of ∼8–9Å surrounded by six trigonal shaped ones with a smaller diameter of ∼4–5Å and thus resembles the structure of HKUST-1.Gas sorption studies revealed that Cu-PEIP exhibits a 1785 m^(2) g^(−1) BET area as well as high CO_(2) sorption capacity(4.75 mmol g^(−1) at 273 K)and CO_(2)/CH4 selectivity(8.5 at zero coverage and 273 K).展开更多
Four novel metal–organic frameworks(MOFs)built from alkaline-earth metal ions and the flexible tetrahedral carboxylate ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid(H_(4)L)were synthesized using solvotherma...Four novel metal–organic frameworks(MOFs)built from alkaline-earth metal ions and the flexible tetrahedral carboxylate ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid(H_(4)L)were synthesized using solvothermal methods.A variety of three-dimensional frameworks were obtained when employing different alkaline earth ions with the formula[Mg_(2)(L)(H_(2)O)(DMA)]·DMA(1),[Ca_(4)(L)_(2)(DMA)_(3)](2),[Ca_(4)(L)_(2)(H_(2)O)_(2)(DMA)_(2)]·(3DMA)(3)and[Sr_(4)(L)_(2)(DMF)_(4)]·(2DMF)(4)reflecting the variation in the ionic radius of alkaline-earth ions as well as the key role of the synthetic conditions used.By removing the vip molecules,a framework shrinking was observed driven by the structural flexibility of the H_(4)L ligand.This resulted in large diffusional resistances towards N_(2)over CO_(2)molecules,therefore leading to a good CO_(2)/N_(2)separation selectivity.Both Ca-based MOFs were very stable up to 98%relative humidity,while Mgand Sr-based MOFs were much less stable.展开更多
基金funded under the M-ERA.NET Call 2019 and the Republic of Cyprus through the Research and Innovation Foundation(contract no:P2P/M-ERA.NET/0319/0005,Acronym:SALMOS)This research has been also funded by the Spanish AEI/MCIN/10.13039/501100011033 within the NextGenerationEU/PRTR funds through the projects PCI2020-112241(M-ERA.NET 2019 project7106,SALMOS)and PID2019-110430 GB-C22(ADLIGHT)+1 种基金European Regional Development Fund(80%)and Andalusian CTEICU/JA in the framework of the Operative Programme FEDER-Andalucia 2014-2020 through projects P20_01258(objective 01)and UPO-1381028(objective 1.2.3.)also contributed to the present researchWe also thank the laboratory of materials characterization INMALAB of Universidad Pablo de Olavide for experiments and technical support.
文摘The synthesis,characterisation and capability to selectively detect vapours of volatile organic compounds(VOCs)and nitroaromatic explosives of a new family of 2-dimensional rare earth(RE)MOFs based on a hexanuclear(RE^(3+))6 secondary building unit(SBU)is reported.The reaction of RE(NO_(3))_(3)with 4,4’-sulfonyldibenzoic acid(H_(2)SDBA)in the presence of 2-fluorobenzoic acid(HFBA)in DMF/MeOH at 100℃afforded compound[RE6(μ_(3)-OH/F)_(8)(SDBA)4(NO_(3))2(H_(2)O)_(6)]_(n)(UCY-15(RE);RE:Y,Eu,Gd,Tb,Dy,Ho,Er).
基金supported by the Cyprus Research Promotion Foundation Grant ΔIΔAKTΩP/0609/43 which is co-funded by the Republic of Cyprus and the European Regional Development Fund.
文摘A new Cu^(2+)complex that was isolated from the initial use of 5-((pyridin-4-ylmethylene)amino)isophthalic acid(PEIPH_(2))in 3d metal–organic framework(MOF)chemistry is reported.Complex{[Cu_(3)(PEIP)_(2)(5-NH_(2)-mBDC)(DMF)]·7DMF}_(∞) denoted as Cu-PEIP·7DMF was isolated from the reaction of Cu(NO_(3))_(2)·2.5H_(2)O with PEIPH_(2) in N,N-dimethylformamide(DMF)at 100℃ and contains both the PEIP2−ligand and its 5-NH_(2)-mBDC2−fragment.After the structure and properties of Cu-PEIP were known an analogous complex was prepared by a rational synthetic method that involved the reaction of Cu(NO_(3))_(2)·2.5H_(2)O,5-((pyridin-4-ylmethyl)amino)isophthalic acid(PIPH_(2)–the reduced analogue of PEIPH_(2))and 5-NH_(2)-mBDCH_(2) in DMF at 100℃.Cu-PEIP comprises two paddle-wheel[Cu_(2)(COO)_(4)]units and exhibits a 3Dframework with a unique trinodal underlying network and point symbol(4.5^(2))_(4)(4^(2)·5^(4)·6^(4)·8^(3)·9^(2))_(2)(5^(2)·8^(4)).This network consists of pillared kgm-a layers containing a hexagonal shaped cavity with a relatively large diameter of ∼8–9Å surrounded by six trigonal shaped ones with a smaller diameter of ∼4–5Å and thus resembles the structure of HKUST-1.Gas sorption studies revealed that Cu-PEIP exhibits a 1785 m^(2) g^(−1) BET area as well as high CO_(2) sorption capacity(4.75 mmol g^(−1) at 273 K)and CO_(2)/CH4 selectivity(8.5 at zero coverage and 273 K).
基金the Advanced Light Source,which is a DOE Office of Science User Facility under contract no.DE-AC02-05CH11231.
文摘Four novel metal–organic frameworks(MOFs)built from alkaline-earth metal ions and the flexible tetrahedral carboxylate ligand tetrakis[4-(carboxyphenyl)oxamethyl]methane acid(H_(4)L)were synthesized using solvothermal methods.A variety of three-dimensional frameworks were obtained when employing different alkaline earth ions with the formula[Mg_(2)(L)(H_(2)O)(DMA)]·DMA(1),[Ca_(4)(L)_(2)(DMA)_(3)](2),[Ca_(4)(L)_(2)(H_(2)O)_(2)(DMA)_(2)]·(3DMA)(3)and[Sr_(4)(L)_(2)(DMF)_(4)]·(2DMF)(4)reflecting the variation in the ionic radius of alkaline-earth ions as well as the key role of the synthetic conditions used.By removing the vip molecules,a framework shrinking was observed driven by the structural flexibility of the H_(4)L ligand.This resulted in large diffusional resistances towards N_(2)over CO_(2)molecules,therefore leading to a good CO_(2)/N_(2)separation selectivity.Both Ca-based MOFs were very stable up to 98%relative humidity,while Mgand Sr-based MOFs were much less stable.
