Construction of sophisticated metal-organic frameworks(MOFs)with multiple kinds of metals is essential for further advancement of porous materials toward various applications.Order and arrangement of the metals in the...Construction of sophisticated metal-organic frameworks(MOFs)with multiple kinds of metals is essential for further advancement of porous materials toward various applications.Order and arrangement of the metals in the secondary building units(SBUs)greatly influence the MOF structures outcome.While most of the previous heterometallic MOFs either have multiple kinds of discrete SBUs with different metals,or single kind of SBU with mixed metals inside,other forms of metal distribution still need further exploration.Herein,a bifunctional linker is applied to achieving differential coordination toward different metals.With Ce and Cu serving as the carboxylate-philic and pyrazole-philic metal ions,three heterometallic MOFs(FDM-121—FDM-123)are synthesized.In addition to the common metal arrangement modes,the new MOFs provide a joint reticulation of a discrete SBU and an infinite chain-like SBU featuring different metals in FDM-121,and an assembly from heterometallic infinite chain-like SBU in FDM-122.This study demonstrates the potential of bifunctional linkers for the design and synthesis of heterometallic MOFs and opens up the possibilities to create MOFs with tailored properties for specific applications.展开更多
Metal-organic frameworks(MOFs)constructed from conjugated organic ligands are candidates for hybrid photoactive materials with potential applications.Compared to that from the ligands only,the intensity and wavelength...Metal-organic frameworks(MOFs)constructed from conjugated organic ligands are candidates for hybrid photoactive materials with potential applications.Compared to that from the ligands only,the intensity and wavelength of the luminescence could be tuned after they were incorporated in extended framework.In this report,by using an organic ligand with azolate moiety,benzo-bis(imidazole)(H2BBI),we synthesized two new MOF structures.Framework 1([Co(H2BBI)(DMSO)2Cl2]n,DMSO=dimethyl sulfoxide),constructed from tetrahedral Co(II)and H2BBI,exhibits zigzag 1D structure.Meanwhile,framework 2([Cu2(H2BBI)3(DMSO)6(NO3)4]n),a layered structure with hcb topology,was assembled from tetragonal pyramidal Cu(II)and H2BBI.Furthermore,2 exhibits strong luminescence emission(ex=280 nm).A blue shift of 40 nm(from 359 nm to 319 nm)was observed in framework 2 compared to the free ligand,which could be explained by the ligand-to-metal charge transfer in the network.展开更多
基金supported by the National Key Research and Development Program of China(No.2018YFA0209402)the National Natural Science Foundation of China(Nos.21922103,21961132003,22088101).
文摘Construction of sophisticated metal-organic frameworks(MOFs)with multiple kinds of metals is essential for further advancement of porous materials toward various applications.Order and arrangement of the metals in the secondary building units(SBUs)greatly influence the MOF structures outcome.While most of the previous heterometallic MOFs either have multiple kinds of discrete SBUs with different metals,or single kind of SBU with mixed metals inside,other forms of metal distribution still need further exploration.Herein,a bifunctional linker is applied to achieving differential coordination toward different metals.With Ce and Cu serving as the carboxylate-philic and pyrazole-philic metal ions,three heterometallic MOFs(FDM-121—FDM-123)are synthesized.In addition to the common metal arrangement modes,the new MOFs provide a joint reticulation of a discrete SBU and an infinite chain-like SBU featuring different metals in FDM-121,and an assembly from heterometallic infinite chain-like SBU in FDM-122.This study demonstrates the potential of bifunctional linkers for the design and synthesis of heterometallic MOFs and opens up the possibilities to create MOFs with tailored properties for specific applications.
基金supported by the National Natural Science Foundation of China(21071032,21101030)Shanghai Pujiang Program(11PJ1400600)the Creative Research Group of Ministry of Education(IRT1117)
文摘Metal-organic frameworks(MOFs)constructed from conjugated organic ligands are candidates for hybrid photoactive materials with potential applications.Compared to that from the ligands only,the intensity and wavelength of the luminescence could be tuned after they were incorporated in extended framework.In this report,by using an organic ligand with azolate moiety,benzo-bis(imidazole)(H2BBI),we synthesized two new MOF structures.Framework 1([Co(H2BBI)(DMSO)2Cl2]n,DMSO=dimethyl sulfoxide),constructed from tetrahedral Co(II)and H2BBI,exhibits zigzag 1D structure.Meanwhile,framework 2([Cu2(H2BBI)3(DMSO)6(NO3)4]n),a layered structure with hcb topology,was assembled from tetragonal pyramidal Cu(II)and H2BBI.Furthermore,2 exhibits strong luminescence emission(ex=280 nm).A blue shift of 40 nm(from 359 nm to 319 nm)was observed in framework 2 compared to the free ligand,which could be explained by the ligand-to-metal charge transfer in the network.
