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Reactions of copper(Ⅱ) sulfate or copper(Ⅱ) perchlorate,samarium(Ⅲ),erbium(Ⅲ) or neodymium(Ⅲ)nitrate(5/1 equiv.) with pyrazinohydroxamic acid(H_2Pyzha) in H_2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H_2O 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(H_2O)_3 {Cu(pyzha)}_5(H_2O)_2(MeOH)(HSO_4)_2]·(H_2O)_2(HSO_4)(1);[Nd(H_2O)_2(MeOH) {Cu(pyzha)}_5(ClO_4)_2(H_2O)_5(NO_3)](2);[Eu(H_2O)_2(MeOH) {Cu(pyzha)}_5(ClO_4)_2(H_2O)_5(NO_3)](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.
Reactions of copper (Ⅱ) sulfate or copper (Ⅱ) perchlorate, samarium (Ⅲ), erbium (Ⅲ) or neodymium (Ⅲ) nitrate (5/1 equiv.) With pyrazinohydroxamic acid (H_2Pyzha) in H_2O / Me0H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH / H 2 O solution, when adding inorganic salts, the ligands exist as protonated metallacrowns. In the solid state, their structures are more confirmed by X-ray analysis: metallacrown [Sm ( H_2O_3 {Cu (pyzha)} _5 (H_2O) _2 (MeOH) (HSO_4) _2] · (H_2O) _2 (HSO_4) (1) (ClO_4) _2 (H_2O) _5 (NO_3)] (2); [Eu (H_2O) _2 (MeOH) {Cu (pyzha)} _5 (ClO_4) _2 (H_2O) _5 of atomic and ionic radii between the encapsulated lanthanide (III) could be used to control the bowl-shape distortion of the metal lacrowns from the planar geometry. The complex 1 clearly exhibited fluorescence behavior of samarium (III), while 2 and 3 show that of copper (Ⅱ) and ligand.