Citation: Yu Wang, Wen-Shi Wu, Miao-Ling Huang. Heterometal-organic frameworks:Three novel copper(II)-lanthanide(III) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platform[J]. Chinese Chemical Letters, ;2016, 27(03): 423-427. doi: 10.1016/j.cclet.2015.12.006 shu

Heterometal-organic frameworks:Three novel copper(II)-lanthanide(III) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platform

1.
College of Materials Science and Engineering, Huaqiao University, Xiamen 361021, China

Corresponding author: Wen-Shi Wu,
Received Date: 21 October 2015
Available Online: 12 November 2015

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/MeOH 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 2 and 3 show that of copper(Ⅱ) and ligand.
- 15-Metallacrown-5,
- Pyrazinohydroxamic acid,
- Heterobimetallic complexes,
- Crystal structures,
- Fluorescence properties
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沈阳化工大学材料科学与工程学院沈阳 110142