Synthesis and Characterization of Coordination Polymers via the Self-assembly of Metal Ions (Co2+, Zn2+, Cd2+), Anionic Ligands (fumarate, isonicotinate, (+, -)tartrate) and Neutral Ligands (4,4-bipy, trans-bpe)

• Main Authors: Ho Chien-Te, 何建德
• Other Authors: Liao Ju-Hsiou
• Format: Others
• Language: zh-TW
• Published: 2001
• Online Access: http://ndltd.ncl.edu.tw/handle/64329972598420078519

碩士 === 國立中正大學 === 化學研究所 === 89 === Seven novel organic-inorganic coordination polymers: Zn(fumarate)(4,4’-bipy)2 (1), [Co(4,4’-bipy)(H2O)4](fumarate)‧4H2O (2), Cd(fumarate)(4,4’-bipy) (3), Cd(isonicotinate)2(trans-bpe)0.5(H2O) (4), [Co(L(+)-tartrate)(4,4’-bipy)(H2O)]2‧(4,4’-bipy) (5) , [Co(D(-)-tartrate)(4,4’-bipy)(H2O)]2‧(4,4’-bipy) (6) and Cd3(NO3)2(isonicotinate)4(4,4’-bipy)2(H2O)2 (7) ( 4,4’-bipy = 4,4’-bipyridine, trans-bpe = trans-1,2-bis(4-pyridyl)-ethylene), were synthesized by pseudo -hydrothermal synthesis and characterized by X-ray crystallographic techniques. (1) crystallizes in monoclinic space group C2/c with a = 18.802(3) Å, b = 10.091(2) Å, c = 14.371(4) Å, β= 125.91(1)°,V = 2208.4(8) Å3. (2) crystallizes in triclinic space group P-1 with a = 7.060(1) Å, b =7.851(2) Å, c = 9.803(1) Å, α= 79.51(1)°, β= 86.63(1)°, γ= 72.59(2)°, V=507.5(2) Å3. (3) crystallizes in monoclinic space group C2/c with a =11.693(1) Å, b = 15.594(2) Å, c = 15.591(1) Å, β= 90.07(1)°, V = 2901.9(5) Å3. (4) crystallizes in triclinic space group P-1 with a = 9.647(1) Å, b = 9.664(1) Å, c = 11.143(2) Å, α= 104.79(1)°, β= 104.75(2)°, γ= 98.30(1)°, V=946.7(2) Å3. (5) crystallizes in monoclinic space group P21 with a = 11.4939(13) Å, b =9.6599(11) Å, c = 18.173(2) Å, β= 107.759(9)°, V = 1921.6(4) Å3. (6) crystallizes in monoclinic space group P21 with a = 11.495(2) Å, b = 9.6654(14) Å, c = 18.170(2) Å, β=107.724(10)°, V =1923.0(5) Å3. (7) crystallizes in monoclinic space group P21/n with a = 9.838(2) Å, b = 12.891(4) Å, c = 19.302(2) Å, β=90.57(2)°, V =2447.8(9) Å3. (1) consists of zigzag chains built up by [Zn(4,4’-bipy)2]2+ moieties linked by fumarate. The structure of (2) consists of one-dimensional chains built up by [Co(H2O)4]2+ units bridged by 4,4’-bipy, with one equivalent of fumarate located between the chains to balance the charge and four equivalents of uncoordinated water molecules. (3) adopts a three-dimensional framework, formed by Cd(fumarate) sheets cross-linked by 4,4’-bipy ligands. (4) is a three-dimensional framework, formed by [Cd(isonicotinate)2(H2O)] motifs cross-linked by 4,4’-bipy ligands. (5) and (6) are enantiomers, consisting of two-dimensional framework, formed by [Cd(tartrate)(H2O)] motifs linked by (4,4’-bipy) ligands, with one equivalent of uncoordinated 4,4’-bipy located between the two-dimensional framework. (7) has two Cd centers. Cd(1) is in a distorted pentagonal bipyrimidal coordination sphere while Cd(2) is in an octahedral environment. Cd(1) and Cd(2) are bridged by 4,4’-bipy and isonicotinate ligands, forming a three-dimensional framework. Their thermal stabilities and spectroscopic data are also reported in the thesis.