Syntheses and Characterizations of Three-Dimensional Channel-like Polymeric Lanthanide Complexes Constructed by 1,2,4,5-Benzenetetracarboxylic Acid

• Published in: Inorganic chemistry Vol. 41; no. 8; pp. 2087 - 2094
• Main Authors: Cao, Rong, Sun, Daofeng, Liang, Yucang, Hong, Maochun, Tatsumi, Kazuyuki, Shi, Qian
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22-04-2002
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic0110124

The hydrothermal reaction of YbCl3·6H2O with 1,2,4,5-benzenetetracarboxylic dianhydride resulted in [{Yb(bbtec)1/4(dbtec)3/6(H2O)2}4·6H2O] n (1) (H4btec = 1,2,4,5-benzenetetracarboxylic acid), and the solvothermal reaction of Er(NO3)3·6H2O or TbCl3·6H2O with 1,2,4,5-benzenetetracarboxylic dianhydride in H2O/acetic acid gave rise to [{Er2(cbtec)2/4(ebtec)2/4(fbtec)2/4(H2O)4}·4H2O] n (2) and [{Tb(H2btec)2/4(fbtec)3/6(H2O)}·2H2O] n (3), respectively. Complex 1 crystallizes in monoclinic space group C2/m with a = 20.8119(5) Å, b = 17.6174(1) Å, c = 5.7252(2) Å, β = 92.324(1)°, and Z = 1. 1 possesses a three-dimensional framework consisting of eight-coordinate ytterbium centers and two kinds of channels along the c axis. Complex 2 crystallizes in triclinic space group P1̄ with a = 9.6739(5) Å, b = 11.0039(5) Å, c = 11.5523 Å, α = 104.8330(10)°, β = 91.0000(10)°, γ = 114.2570(10)°, and Z = 2. 2 has a three-dimensional framework comprising both eight- and nine-coordinate erbium centers and channels along the a axis. Complex 3 crystallizes in monoclinic space group P21/n with a = 10.7246(12) Å, b = 7.1693(9) Å, c = 17.158(2) Å, β = 97.109(2)°, and Z = 4. 3 shows a three-dimensional framework containing nine-coordinate terbium centers and channels along the b axis. Uncoordinated water molecules occupy the channels in the three complexes. TGA and XRPD were determined for the three complexes, and the results illustrate that the framework of 1 is retained upon removal of uncoordinated and coordinated water molecules.