含N,N′-二-(4-吡啶)己二醯二胺配位基與二價鈷金屬化合物之合成,結構與特性研究

Synthesis, Structures and Properties of Cobalt (II) Complexes Containing N-N′-di-(4-pyridyl)adipoamide Ligand

許晉瑋(Chin-Wei Hsu)

指導教授 ： 陳志德

中原大學/理學院/化學研究所/碩士(2010年)

https://doi.org/10.6840/cycu201000747

摘要

本論文主要討論含 N,N′-二-(4-吡啶)己二醯二胺配位基與二價鈷金屬之化學。將配位基 N,N′-二-(4-吡啶)己二醯二胺(L)與二價鈷金屬反應可以得到化合物[Co2Cl4(L)2]．OEt, 1, [Co2X4(L)2]．CH3OH, (X = Br, 2 and I, 3) and {[Co(L)2(C2H5O)2](ClO4)2}∞, 4。以上化合物都以單晶X-ray繞射儀來鑑定其單晶結構。錯合物1、2和3皆形成0D的雙核環狀結構，且由奈米尺寸之Co2L2矩形分子格所組成，其孔洞大小在錯合物1 - 3中分別為9.49 × 6.33 Å2、8.85 × 7.32 Å2與8.56 × 8.57 Å2。錯合物1 - 3的0D雙核金屬圓環結構中透過N-H---O氫鍵作用力形成1D的超分子結構。這種1D的超分子結構再藉由N-H---X (X = Cl, 1, Br, 2 and I, 3)氫原子到鹵素的作用力相互連結形成2D的層狀超分子結構。錯合物4形成3-fold 2D parallel interpenetrating sheets，最後可以得到7-fold interpenetrated 3D 網狀結構。配位基L與金屬鍵結後，有不同的構形，在錯合物1 - 3中是AAG cis的構形，錯合物4中則是AAA trans及AGA trans的構形。

關鍵字

二價鈷 ； 環狀雙核 ； 孔洞

並列摘要

This thesis discusses the chemistry of cobalt(II) complexes containing N-N′-di-(4-pyridyl)adipoamide ligand. A series of Co(II) complexes with N-N′-di-(4-pyridyl)adipoamide ligand(L), [Co2Cl4(L)2]．OEt, 1, [Co2X4(L)2]．CH3OH, (X = Br, 2 and I, 3) and {[Co(L)2(C2H5O)2](ClO4)2}∞, 4, have been prepared by the reactions of L with Co(II) salts and their structures have been determind by X-ray crystallography. Complexes 1, 2 and 3 show the 0D dimeric structures with nanoporous Co2L2 rectangle metallocycles and the approximately accessible cavity sizes are 9.49 × 6.33 Å2 for 1, 8.85 × 7.32 Å2 for 2 and 8.56 × 8.57 Å2 for 3, respectively. Those dinuclear metallocycles in complexes 1 – 3 are linked together through N-H---O hydrogen bonds to form 1D supramolecular structures, which are further linked by N-H---X (X = Cl, 1, Br, 2 and I, 3) hydrogen bonds to form 2D supramolecular layers. Complex 4 forms parallel interpenetrations of 3-fold 2D parallel interpenetrating sheets, resulting in a 7-fold interpenetrated 3D network. The L ligand in complexes 1 - 3 adopts the AAG cis comformation and those in complex 4 adopt the AAA trans and AGA trans comformations.

並列關鍵字

N-N′-di-(4-pyridyl)adipoamide ； coodination polymer ； cobalt

參考文獻

[9] Z. Spichal, M. Necas, J. Pinkas, Inorg. Chem., 2005, 44, 2074.

[11] (a) S. Noro, S. Kitagawa, M. Kondo, K. Seki, Angew. Chem. Int. Ed., 2000, 39, 2082. (b) M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O’Keeffe, O. M. Yaghi, Science., 2002, 295, 469.

[13] M. Fujita; J. Yazaki, K. Ogura, J. Am. Chem. Soc., 1990, 112, 5645.

[14] T.-Y. Chang , Master's Thesis, 2008.

[15] O. M. Yaghi, H. Li, T. L. Groy, Inorg. Chem., 1997, 36, 4292.