腙基萘啶之鋅、銀錯合物的金屬超分子

Metallo-supramolecules Based on Zinc and Silver Complexes with Naphthyridine-Dimine Ligand

魏君如(Chun-Ju Wei)

指導教授 ： 王文竹

淡江大學/理學院/化學學系碩士班/碩士(2008年)

https://doi.org/10.6846/TKU.2008.01122

摘要

合成出一系列含腙基架橋的萘啶配位子，及其與鋅 ( II ) 反應形成三明治結構的錯合物 [Zn2(C2-Me-(Dmenpt)2)2(OH)2(CH3OH)2](ClO4)2 1 、[Zn2(C2-H-(Dmenpt)2)2(OH)2(H2O)2](ClO4)2 2 ，以及平面結構錯合物[Zn(Py-Me-(Dmenpt)2)(CH3OH)2](ClO4)2 3、 [Zn(C2-Me-(Npt)2)(CH3OH)2] (ClO4)2 4 ，與銀 ( I ) 反應形成四核雙螺旋結構[Ag4(C2-Me-(Npt)2)2] (CF3SO3)4 5 ，藉由 X-ray 繞射來解析所得到的錯合物的結構，我們亦可藉由 ESI-Mass 來作此自組裝錯合物之定性分析，藉此可幫助我們鑑定且了解此系列錯合物在溶液態中的組成，也可分析在溶液態中的組成與固態時的表現是否相同。
利用鋅鹽滴定配位子的 UV-Vis 滴定實驗探討在溶液中，形成錯合物時金屬與配位子的當量比，以及分子自組裝的過程，建立反應機構及求得熱力學穩定常數。並且再利用配位子 1 、 2 反滴定鋅鹽得到相同的結果，檢視其具有自我辨識的能力。並且由反滴定實驗以及發射光譜得知，當溶液中分子濃度增加時，由於分子間 π-π 作用力，而形成聚集現象。
我們也利用電子吸收光譜及發射光譜，探討配位子以及錯合物的發光機制。

關鍵字

超分子 ； 自我組裝 ； 鋅錯合物 ； 銀錯合物 ； 聚集

並列摘要

In this research, a series of new ligands containing hydrazone and derivative naphthyridine moiety were synthesized successfully, after complexed with binding Zn (II) , gives sandwich like complexes , namely, [Zn2(C2-Me-(Dmenpt)2)2(OH)2(CH3OH)2](ClO4)2 1 、[Zn2(C2-H-(Dmenpt)2)2(OH)2(H2O)2](ClO4)2 2 ，and planar structure ，[Zn(Py-Me-(Dmenpt)2)(CH3OH)2](ClO4)2 3 、 [Zn(C2-Me-(Npt)2)(CH3OH)2](ClO4)2 4， and complexes with silver(I) to formed tetranuclear helicate , namely, [Ag4(C2-Me-(Npt)2)2](CF3SO3)4 5 .The crystal structures of the complexes have been determined by X-ray analysis﹐and ESI-Mass spectrometry proved a very useful characterisational tool in detecting the distribution of complexes in solution﹐the results confirmed the solid state is maintained in the solution state.
The self-assembling and self-recognition process were studied by UV-Vis titration, and were investigated by means of systematic measurement of step-wise and overall stability constant .
We present molecular self-assembly system﹐driven mostly by π-π interactions﹒The formation of such self-organization is characterized with absorption and fluorescence spectroscopies﹒Our results demonstrate that molecules can promote self-organization in solution.
The flourescence spectra of ligands and complexes haved been investigated.

並列關鍵字

Supramolecule ； Zinc ； Silver ； Self-assembly ； Hydrazone-Naphthyridine

參考文獻

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