The combination of a zirconium metal-organic cluster and a Keggin type polyoxotungstate into a compound of the formula[Zr_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(μ-OOCC_(6)H_(5))_(8)(H_(2)O)_(8)][SiW_(12)O_(4)0]led to a che...The combination of a zirconium metal-organic cluster and a Keggin type polyoxotungstate into a compound of the formula[Zr_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(μ-OOCC_(6)H_(5))_(8)(H_(2)O)_(8)][SiW_(12)O_(4)0]led to a chemically and photochemically stable material in which a synergistic effect between the metal-organic cluster and the polyoxometalate allows marked enhancement of the photochemical activity of the single ionic components toward the photooxidation of dyes.展开更多
UiO-66,reported in 2008,inspired the ongoing chemistry of group 4 metal–organic frameworks and it is still one of the most studied MOFs due to its exceptional stability.The tightness of their building blocks and bond...UiO-66,reported in 2008,inspired the ongoing chemistry of group 4 metal–organic frameworks and it is still one of the most studied MOFs due to its exceptional stability.The tightness of their building blocks and bond strength make it tough to access new topologies,unless the building blocks are changed or defect engineering is employed,which in turn lead to different nominal stoichiometries.However,well selected structure directing agents and harsh synthesis conditions allowed the isolation of the first polymorph of UiO-66,named EHU-30.Herein,we provide evidence for the generalization of the synthetic approach with four new EHU-30 isoreticular compounds,based on amino-functionalized linkers and zirconium and hafnium as metal centres:EHU-30-NH_(2)(M)and EHU-30-NHR(M)(M:Zr,Hf;R:2-carboxypropyl).The crystal structure analysis reveals that their framework is more porous than that of their polymorphic counterpart.Furthermore,due to the current relevance of MOFs in greenhouse gas capture and in water harvesting methodologies,we have explored CO_(2)and water vapour adsorption on the new polymorphic phases,by means of experimental and computational resources,and compared to the parent EHU-30.The amino functionalization makes the EHU-30 series more prone to CO_(2)and water vapour adsorption.Besides,the water adsorption isotherms show an interesting crossing sensitive to temperature,sorption cycles and functionalization of the linker,which has been attributed to a localized structural transformation from EHU-30 to UiO-66.Finally,time-of-flight(TOF)powder neutron diffraction experiments were also conducted to locate the preferred adsorption sites for water in functionalized and parent EHU-30 structures.展开更多
Herein we prove the efficiency of the oven heating solvent-free synthesis,based on the acid-base reaction between a metal oxide/hydroxide,adenine(HAde)and monocarboxylic acids,to afford otherwise not accessible new MB...Herein we prove the efficiency of the oven heating solvent-free synthesis,based on the acid-base reaction between a metal oxide/hydroxide,adenine(HAde)and monocarboxylic acids,to afford otherwise not accessible new MBioFs of formula[M2(μ3-Ade)2(μ2-OOC(CH_(2))_(x)CH_(3))_(2)]n expressed as 1_M@monocarboxylate[M(II):Ni or Zn;monocarboxylate:butanoato(But)and propanoato(Prop)].Additionally,a microwave assisted solvent-free procedure has been carried out,leading to products with a somewhat lower adsorption performance but with the advantages of reducing the reaction times to the minute scale and incorporating randomly distributed additional meso/macropores generated during the release of the water vapour by-product.Both heating techniques provide the resulting products in a monolithic form.The N2(77 K)and CO_(2)(273 K)adsorption isotherms indicate a great selectivity towards CO_(2)for the 1_Ni@But compound.On the other hand,a careful control over the solvent-free conditions provided good-quality single crystals of three new compounds based on the metal/nucleobase/carboxylate system:[Zn3(μ3-Ade)2(μ-OOCCH_(3))_(4)]n·3H_(2)O(2),[Zn(μ-Hypo)(μ-OOCCH_(3))]n(3)(Hypo:hypoxanthinate)and[Ni2(μ-HAde)2(μ-OOCH)2(OOCH)2(OH_(2))2]·2{(H_(2)Ade)(HCOO)}·2HCOOH(4).Compounds 2 and 3 show lamellar structures without accessible voids.Compound 4 represents an intermediate stage between the initial reagent mixture and the final extended coordination polymers that depicts an insight into the reaction mechanism of the solvent-free approach.It also shows the difficulties in stabilizing the porous structure of 1 when short aliphatic monocarboxylic acids,such as acetic and formic acids,are employed.展开更多
Herein we explore the opportunities arising from combining magnetic properties and porosity in metal-organic materials.In this sense,we have prepared an adenine based homometallic wheel-shaped heptameric[Cu_(7)(μ-ade...Herein we explore the opportunities arising from combining magnetic properties and porosity in metal-organic materials.In this sense,we have prepared an adenine based homometallic wheel-shaped heptameric[Cu_(7)(μ-adeninato)_(6)(μ_(3)-OH)_(6)(μ-OH_(2))_(4)]^(2+)entity containing two metal coordination environments:CuO_(6)at the core of the wheel with an unusually modest Jahn-Teller distortion and six peripheral CuN_(2)O_(4)with a more pronounced elongation.展开更多
Correction for‘An in solution adsorption characterization technique based on the response to an external magnetic field of porous paramagnetic materials:application on supramolecular metal-adenine frameworks containi...Correction for‘An in solution adsorption characterization technique based on the response to an external magnetic field of porous paramagnetic materials:application on supramolecular metal-adenine frameworks containing heterometallic heptameric clusters’by Jon Pascual-Colino et al.,Inorg.Chem.Front.,2023,https://doi.org/10.1039/d2qi01994a.展开更多
基金financial support from the Basque Government(IT1291-19)from the University of the Basque Country(predoctoral fellowships for J.P.C.and M.P.I.:PIF17/51 and PIF18/175)+1 种基金from the Spanish Ministry of Science and Innovation(PID2019-108028GB-C21)Technical and human support provided by SGIker(UPV/EHU,MICINN,GV/EJ,and ESF)is also acknowledged.
文摘The combination of a zirconium metal-organic cluster and a Keggin type polyoxotungstate into a compound of the formula[Zr_(6)(μ_(3)-O)_(4)(μ_(3)-OH)_(4)(μ-OOCC_(6)H_(5))_(8)(H_(2)O)_(8)][SiW_(12)O_(4)0]led to a chemically and photochemically stable material in which a synergistic effect between the metal-organic cluster and the polyoxometalate allows marked enhancement of the photochemical activity of the single ionic components toward the photooxidation of dyes.
基金the financial support from the Basque Government(IT1291-19)from the Spanish Ministry of Science and Innovation(PID2019-108028GB-C21,CTQ2017-92173-EXP and IJC2018-038162-I)+2 种基金Technical and human support provided by SGIker(UPV/EHU,MICINN,GV/EJ,and ESF)HPC support from C3UPO are also acknowledgedthe ISIS Neutron and Muon Source for the award of beam time on GEM(experiment RB1920440).
文摘UiO-66,reported in 2008,inspired the ongoing chemistry of group 4 metal–organic frameworks and it is still one of the most studied MOFs due to its exceptional stability.The tightness of their building blocks and bond strength make it tough to access new topologies,unless the building blocks are changed or defect engineering is employed,which in turn lead to different nominal stoichiometries.However,well selected structure directing agents and harsh synthesis conditions allowed the isolation of the first polymorph of UiO-66,named EHU-30.Herein,we provide evidence for the generalization of the synthetic approach with four new EHU-30 isoreticular compounds,based on amino-functionalized linkers and zirconium and hafnium as metal centres:EHU-30-NH_(2)(M)and EHU-30-NHR(M)(M:Zr,Hf;R:2-carboxypropyl).The crystal structure analysis reveals that their framework is more porous than that of their polymorphic counterpart.Furthermore,due to the current relevance of MOFs in greenhouse gas capture and in water harvesting methodologies,we have explored CO_(2)and water vapour adsorption on the new polymorphic phases,by means of experimental and computational resources,and compared to the parent EHU-30.The amino functionalization makes the EHU-30 series more prone to CO_(2)and water vapour adsorption.Besides,the water adsorption isotherms show an interesting crossing sensitive to temperature,sorption cycles and functionalization of the linker,which has been attributed to a localized structural transformation from EHU-30 to UiO-66.Finally,time-of-flight(TOF)powder neutron diffraction experiments were also conducted to locate the preferred adsorption sites for water in functionalized and parent EHU-30 structures.
基金funded by the Ministerio de Economía y Competitividad(MAT2013-46502-C2-1-P)Eusko Jaurlaritza/Gobierno Vasco(grant IT477-10 and S-PE13UN016)UPV/EHU(UFI 11/53,EHUA14/09,postdoctoral fellowship for S.P.Y.).Technical and human support provided by SGIKer(UPV/EHU,MINECO,GV/EJ,ERDF,and ESF)is gratefully acknowledged.
文摘Herein we prove the efficiency of the oven heating solvent-free synthesis,based on the acid-base reaction between a metal oxide/hydroxide,adenine(HAde)and monocarboxylic acids,to afford otherwise not accessible new MBioFs of formula[M2(μ3-Ade)2(μ2-OOC(CH_(2))_(x)CH_(3))_(2)]n expressed as 1_M@monocarboxylate[M(II):Ni or Zn;monocarboxylate:butanoato(But)and propanoato(Prop)].Additionally,a microwave assisted solvent-free procedure has been carried out,leading to products with a somewhat lower adsorption performance but with the advantages of reducing the reaction times to the minute scale and incorporating randomly distributed additional meso/macropores generated during the release of the water vapour by-product.Both heating techniques provide the resulting products in a monolithic form.The N2(77 K)and CO_(2)(273 K)adsorption isotherms indicate a great selectivity towards CO_(2)for the 1_Ni@But compound.On the other hand,a careful control over the solvent-free conditions provided good-quality single crystals of three new compounds based on the metal/nucleobase/carboxylate system:[Zn3(μ3-Ade)2(μ-OOCCH_(3))_(4)]n·3H_(2)O(2),[Zn(μ-Hypo)(μ-OOCCH_(3))]n(3)(Hypo:hypoxanthinate)and[Ni2(μ-HAde)2(μ-OOCH)2(OOCH)2(OH_(2))2]·2{(H_(2)Ade)(HCOO)}·2HCOOH(4).Compounds 2 and 3 show lamellar structures without accessible voids.Compound 4 represents an intermediate stage between the initial reagent mixture and the final extended coordination polymers that depicts an insight into the reaction mechanism of the solvent-free approach.It also shows the difficulties in stabilizing the porous structure of 1 when short aliphatic monocarboxylic acids,such as acetic and formic acids,are employed.
基金funded by Eusko Jaurlaritza/Gobierno Vasco(IT1291-19,IT1722-22,ELKARTEK program KK-2022/00109)Ministerio de Universidades and the European Union-Next Generation EU(marsa21/52,R.P.A.)+1 种基金Ministerio de Ciencia e Innovación(PID2019-108028GB-C21)Technical and human support provided by SGIker(UPV/EHU,MICINN,GV/EJ,ESF)is also acknowledged.
文摘Herein we explore the opportunities arising from combining magnetic properties and porosity in metal-organic materials.In this sense,we have prepared an adenine based homometallic wheel-shaped heptameric[Cu_(7)(μ-adeninato)_(6)(μ_(3)-OH)_(6)(μ-OH_(2))_(4)]^(2+)entity containing two metal coordination environments:CuO_(6)at the core of the wheel with an unusually modest Jahn-Teller distortion and six peripheral CuN_(2)O_(4)with a more pronounced elongation.
文摘Correction for‘An in solution adsorption characterization technique based on the response to an external magnetic field of porous paramagnetic materials:application on supramolecular metal-adenine frameworks containing heterometallic heptameric clusters’by Jon Pascual-Colino et al.,Inorg.Chem.Front.,2023,https://doi.org/10.1039/d2qi01994a.
