利用水熱合成含吡啶雙羧酸及草酸之釔(Ⅲ)金屬配位聚合物及其結構分析

Hydrothermal Synthesis and Structure of the Yttrium (Ⅲ) Coordination Polymer Based on Pyridinedicarboxylate and Oxalate

沈福銘(Fwu-Ming Shen))

《元培學報》 14期 (2007/12) Pp. 13-24

https://doi.org/10.30171/JYUST.200712.0002

摘要

將吡啶－2,4-雙羧酸加Y(NO3)3•6H2O及4,4'-雙吡啶加水混合，利用水熱合成，得到釔(Ⅲ)的配位聚合物，其化學式爲[Y2(pda)(C2O4)0.5(H2O)3.5］(下标 ∞)(1)（pda=吡啶－2,4-雙羧酸）。利用X-Ray晶體繞射儀及FT-IR光譜儀測定產物晶體結構及性質，結果顯示錯合物含有草酸的橋鍵配位基，此草酸配基來自吡啶－2,4-雙羧酸上的羧酸基，經由C-C鍵的裂解產生CO2分子，CO2分子經由電子轉移產生二氧化碳自由基，兩個二氧化碳自由基再經由還原偶合產生草酸根離子。化合物1爲2-D的配位聚合物，由於吡啶雙羧酸以及配位水分子，因分子間的氫鍵作用，以及吡啶環之間的π-π吸引力，使得此晶體自組裝成3-D無限延伸的網狀結構。

關鍵字

水熱合成 ； 吡啶－2,4-雙羧酸 ； 4,4'-雙吡啶 ； 氫鍵

並列摘要

A new complex, [Y2(pda) (C2O4)0.5(H2O)3.5](subscript ∞) (1) (pda=pyridine-2,4-dicarboxylate), is hydrothermal synthesized from the reaction of Y(NO3)3•6H2O, pdaH2, and 4,4'-bipyridine. Compound 1 is fully characterized by FT-infrared and single crystal X-ray diffraction. X-ray structure analyses show that both polymers contain bridging oxalate (C2O4^(-2)) ligands, which might have been formed by the reductive coupling of CO2 molecules released from the pda ligands through the C-C bond cleavage. The 2-D coordination polymers were assembled into 3-D networks via O-H…O hydrogen bond and π-π stacking interactions.

並列關鍵字

Hydrothermal Synthesis ； Pyridine-2,4-dicarboxylic acid ； 4,4'-Bipyridine ； Hydrogen Bonding