One dimensional metallophosphate coordination polymers{[M(dtbp)_(2)(azopy)(H_(2)O)_(2)]·(azopy)}_(x)(M=Mn(1);Co(2);Cu(3);Cd(4))have been synthesized from the reaction of a suitable metal precursor with di-tert-bu...One dimensional metallophosphate coordination polymers{[M(dtbp)_(2)(azopy)(H_(2)O)_(2)]·(azopy)}_(x)(M=Mn(1);Co(2);Cu(3);Cd(4))have been synthesized from the reaction of a suitable metal precursor with di-tert-butylphosphate(dtbp-H)in the presence of ditopic linker 4,4’-azobipyridine(azopy)in a 1:2:2 stoichiometric ratio.Isostructural compounds 1–4 have been characterized by analytical and spectroscopic methods and single crystal X-ray diffraction studies.Single crystal X-ray diffraction measurements further reveal that compounds 1–3(all C2/c)and 4(P1)are linear 1D coordination polymers.The uncoordinated 4,4’-azobipyridine in the lattice is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O–H⋯N hydrogen bonding interactions between coordinated water and N-centers of an azopy ligand.Similar reactions carried out using 1,2-bis(4-pyridyl)-ethylene(bpe)as the linker yielded compounds having the formula{[M(dtbp)_(2)(bpe)(H_(2)O)_(2)]·(bpe)}_(x)(M=Mn(5);Co(6);Cu(7);Ni(8)).Compounds 5–8 have been characterized by analytical and spectroscopic methods.Preliminary single crystal X-ray diffraction studies carried out on poorly diffracting crystals of 5 and 6 establish their isostructural nature to 1–4,also displaying a similar supramolecular aggregation behaviour.A longer ditopic N,N’-donor ligand,1,2-bis(pyridin-3-ylmethylene)hydrazine(bph),has been used in place of bpe/azoby to synthesize 1-dimensional coordination polymers[{M(bph)(H_(2)O)_(4)}{(dtbp)_(2)}](M=Ni(9)and M=Co(10))and[Cd(bph)_(3)(dtbp)_(2)]_(n)(11)which have completely different structural motifs when compared to 1–4.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
文摘One dimensional metallophosphate coordination polymers{[M(dtbp)_(2)(azopy)(H_(2)O)_(2)]·(azopy)}_(x)(M=Mn(1);Co(2);Cu(3);Cd(4))have been synthesized from the reaction of a suitable metal precursor with di-tert-butylphosphate(dtbp-H)in the presence of ditopic linker 4,4’-azobipyridine(azopy)in a 1:2:2 stoichiometric ratio.Isostructural compounds 1–4 have been characterized by analytical and spectroscopic methods and single crystal X-ray diffraction studies.Single crystal X-ray diffraction measurements further reveal that compounds 1–3(all C2/c)and 4(P1)are linear 1D coordination polymers.The uncoordinated 4,4’-azobipyridine in the lattice is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O–H⋯N hydrogen bonding interactions between coordinated water and N-centers of an azopy ligand.Similar reactions carried out using 1,2-bis(4-pyridyl)-ethylene(bpe)as the linker yielded compounds having the formula{[M(dtbp)_(2)(bpe)(H_(2)O)_(2)]·(bpe)}_(x)(M=Mn(5);Co(6);Cu(7);Ni(8)).Compounds 5–8 have been characterized by analytical and spectroscopic methods.Preliminary single crystal X-ray diffraction studies carried out on poorly diffracting crystals of 5 and 6 establish their isostructural nature to 1–4,also displaying a similar supramolecular aggregation behaviour.A longer ditopic N,N’-donor ligand,1,2-bis(pyridin-3-ylmethylene)hydrazine(bph),has been used in place of bpe/azoby to synthesize 1-dimensional coordination polymers[{M(bph)(H_(2)O)_(4)}{(dtbp)_(2)}](M=Ni(9)and M=Co(10))and[Cd(bph)_(3)(dtbp)_(2)]_(n)(11)which have completely different structural motifs when compared to 1–4.
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).
