含雙醯胺吡啶配位基與二價銅金屬化合物之合成、結構與配位基構型研究

Copper (II) Complexes Containing Dipyridyl Ligands Bearing Amide Groups: Syntheses, Structures and Ligand Conformations

朱陳郁涵(Chu Chen, Yu-Han)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2011年)

https://doi.org/10.6840/cycu201100432

摘要

本論文主旨在於探討含雙醯胺吡啶配位基與二價銅金屬鹽類所合成之晶體結構之化學。將硫酸銅分別與配位基N-N’-二-(4-吡啶)己二醯二胺(L1)以及N-N’-二-(4-吡啶)辛二醯二胺(L2)以溶劑熱法反應，可以得到二維高分子層狀結構[CuSO4(L1)(CH3OH)]∞，1，和[CuSO4(L2)2(CH3OH)4]∞，2；另外再利用配位基N-N’-二-(4-吡啶)辛二醯二胺(L2)與帶有三個結晶水的硝酸銅在室溫下反應，可以得到一維高分子鏈[Cu(NO3)2(L2)(CH3OH)]∞，3，以上錯合物均以X-光單晶繞射儀鑑定其單晶結構，並用光譜儀分析之。
錯合物1為二維高分子層狀結構，其層間經由O-H---O及N-H---O氫鍵作用力形成三維超分子架構。在錯合物2中，金屬與配位基形成一維螺旋鏈，再藉由硫酸根陰離子連接形成二維高分子層狀結構，三層獨立的結構彼此間互相穿透，進而形成三層交互貫穿的二維層狀結構，鄰近的層與層間藉由N-H---O氫鍵作用力形成三維超分子架構。而錯合物3形成一維高分子鏈狀結構，一維鏈間透過N-H---O、O-H---O以及C-H---O等氫鍵作用力在空間中堆疊，形成三為超分子結構。此外，錯合物1、2、3之配位基皆呈現不同的構型，錯合物1為AGA trans的構型；錯合物2則有AAGAA cis和AGGGA cis兩種構型；錯合物3則呈現AGAGA trans的構型。

關鍵字

構型 ； 銅 ； 雙醯胺吡啶

並列摘要

This thesis discusses the chemistry of copper(II) complexes containing dipyridyl ligands bearing amide groups. The reactions of the N-N’-di-(4-pyridyl)adipoamide ligand (L1) and N-N’-di-(4-pyridyl)suberoamide ligand (L2) with copper sulfate by solvothermal method afforded the two-dimensional polymeric nets [CuSO4(L1)(CH3OH)]∞, 1, and [CuSO4(L2)2(CH3OH)4]∞, 2, respectively. The reactions of the N-N’-di-(4-pyridyl)suberoamide ligand (L2) with copper nitrate at room temperature gave the one-dimensional polymeric chain [Cu(NO3)2(L2)(CH3OH)]∞, 3. All complexes have been structurally characterized by spectroscopic methods.
In complex 1, a series of O-H---O and N-H---O hydrogen bonds were found between the two-dimensional polymeric nets, forming a three-dimensional supramolecular framework. In complex 2, the cooper(II) centers are linked through L2 ligands to give a one-dimensional infinite helical chains, which are further linked by sulfate anions to form two-dimensional polymeric nets. Three independent nets interpenetrate to each other to give a three-fold interpenetration. The adjacent nets are linked by N-H---O hydrogen bonds, to give a three-dimensional supramolecular framework. Complex 3 forms polymeric one-dimensional chains, which are linked to each other by N-H---O, O-H---O and C-H---O hydrogen bonds to form a three-dimensional supramolecular framework. Moreover, the ligands adopt different conformations in complexes. In complex 1, the L1 ligand adopts AGA trans conformation. The L2 ligand adopts AAGAA cis and AGGGA cis conformations in the complex 2 and those in 3 adopts AGAGA trans conformation.

並列關鍵字

Conformation ； Copper ； Dipyridyl Ligand

參考文獻

[ 22 ] Zhang, L.; Tang, L. F.; Wang, Z. H.; Du, M.; Julve, M.; Lloret, F.; Wang, J. T. Inorg. Chem., 2001, 40, 3619.

[ 41 ] Chen, H. C.; Hu, H. L.; Chan, Z. K.; Yeh, C. W.; Jia, H.W.; Wu, C.P.; Chen, J. D.; Wang, J. C. Cryst. Growth Des., 2007, 7, 698.

[ 10 ] Hsu, Y. F.; Hsu, W.; Wu, C. J.; Cheng, P. C.; Yeh, C. W.; Chang, W. J.; Chen, J. D.; Wang, J. C. CrystEngComm., 2010, 12, 702.

[ 12 ] (a) Li, S. H.; Gao, S. K.; Liu, S. X.; Guo, Y. N. Cryst. Growth Des., 2010, 10, 495. (b) Yeh, C. W.; Chen, J. D.; Wang, J. C. Polyhedron, 2008, 27, 3611.

[ 29 ] Feng, L.; Chen, Z.; Liao, T.; Li, P.; Jia, Y.; Liu, X.; Yang, Y.; Zhou, Y. Cryst. Growth Des., 2009, 9, 1505.