Reactions of copper(Ⅱ) sulfate or copper(Ⅱ) perchlorate,samarium(Ⅲ),erbium(Ⅲ) or neodymium(Ⅲ)nitrate(5/1 equiv.) with pyrazinohydroxamic acid(H2Pyzha) in H2O/Me0 H led to three new heterobimetallic ...Reactions of copper(Ⅱ) sulfate or copper(Ⅱ) perchlorate,samarium(Ⅲ),erbium(Ⅲ) or neodymium(Ⅲ)nitrate(5/1 equiv.) with pyrazinohydroxamic acid(H2Pyzha) in H2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H2O solution,when adding inorganic salts,the ligands exist as protonated metallacrowns.In the solid state,their structures are more complicated as confirmed by X-ray analysis:metallacrown[Sm(H2O)3 {Cu(pyzha)}5(H2O)2(MeOH)(HSO4)2]·(H2O)2(HSO4)(1);[Nd(H2O)2(MeOH) {Cu(pyzha)}5(ClO4)2(H2O)5(NO3)](2);[Eu(H2O)2(MeOH) {Cu(pyzha)}5(ClO4)2(H2O)5(NO3)](3).The differentiation of atomic and ionic radii between the encapsulated lanthanide(Ⅲ) could be used to control the bowl-shape distortion of the metallacrowns from the planar geometry.The complex 1 clearly exhibits fluorescence behavior of samarium(Ⅲ),while 2and 3 show that of copper(Ⅱ) and ligand.展开更多
文摘Reactions of copper(Ⅱ) sulfate or copper(Ⅱ) perchlorate,samarium(Ⅲ),erbium(Ⅲ) or neodymium(Ⅲ)nitrate(5/1 equiv.) with pyrazinohydroxamic acid(H2Pyzha) in H2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H2O solution,when adding inorganic salts,the ligands exist as protonated metallacrowns.In the solid state,their structures are more complicated as confirmed by X-ray analysis:metallacrown[Sm(H2O)3 {Cu(pyzha)}5(H2O)2(MeOH)(HSO4)2]·(H2O)2(HSO4)(1);[Nd(H2O)2(MeOH) {Cu(pyzha)}5(ClO4)2(H2O)5(NO3)](2);[Eu(H2O)2(MeOH) {Cu(pyzha)}5(ClO4)2(H2O)5(NO3)](3).The differentiation of atomic and ionic radii between the encapsulated lanthanide(Ⅲ) could be used to control the bowl-shape distortion of the metallacrowns from the planar geometry.The complex 1 clearly exhibits fluorescence behavior of samarium(Ⅲ),while 2and 3 show that of copper(Ⅱ) and ligand.