含吡啶腙基配位子銀錯合物之金屬超分子研究

Metallo-Supranolecules Based on Silver Complexes with Pyridine-Hydrazone Deviative Ligands

李俊暉(Chun-Hui Li)

指導教授 ： 王文竹

淡江大學/理學院/化學學系碩士班/碩士(2014年)

https://doi.org/10.6846/TKU.2014.00119

摘要

在本研究中，合成了亞胺腙基吡啶型配位子L1、L2、L3、L4以及L5，與銀離子配位得到[Ag2L22](BF4)2 (1)、{[Ag4L32(H2O)2](BF4)4•2H2O}∞ (2)、[Ag3L52]2(PF6)5 (3)、[Ag2L52](PF6)2 (4)對其特性進行研究。

L2可與銀鹽形成Ag2L2的錯合物(1)，配位子上氧原子擔任架橋同時配位兩個銀離子；L3可與銀鹽進一步形成coordination polymer的錯合物(2)；L5根據合成方式的不同，能夠形成雙核以及三核的雙股螺旋錯合物，並且銀-銀距離皆小於銀離子凡得瓦半徑合，靠著分子間的π-π作用力進一步形成無限的一維金屬線

L5的核磁共振光譜滴定實驗與錯合物3的核磁共振光譜比較，觀察出即使錯合物是Ag3L52
，在溶液態中需要更大量的銀才能維持穩定的結構，並且藉由變溫核磁共振光譜實驗可得知溫度的改變會使錯合物2、3的結構扭曲。

在研究分子自組裝方面，利用UV-Vis滴定測量以銀鹽滴定配位子的光譜變化，再以SPECFIT計算得知分子的反應機制是以L、AgL、AgL2、Ag4L2、。

固態結構與自組裝反應的實驗結果一致，證明此系列的配位子在與銀形成錯合物時，可自組裝形成穩定的錯合物。

關鍵字

超分子 ； 銀錯合物 ； 自組裝 ； 螺旋錯合物 ； 腙基

並列摘要

In this research, a series of new ligands (L1、L2、L3、L4 and L5) containing hydrazone and derivative pyridine moiety were synthesized. Four silver complexes, [Ag2L22](BF4)2 (1)、{[Ag4L32(H2O)2](BF4)4•2H2O}∞ (2)、[Ag3L52]2(PF6)5 (3)、[Ag2L52](PF6)2 (4) have been prepared and characterized by X-ray diffraction study.

Complex 1 synthesis from L2 and silver salt, the oxygen atoms were bridge two silver ions. Complex 2 can further form coordination polymer. According to different synthesis, L5 can form Ag3L52 and Ag2L52 complexes. The Ag-Ag distance smaller than the sum of Van der Waals radii of silver ion. The π−π stacking interaction to form polymeric superstructure.

Compare with NMR titration of L5 and NMR of complex 3, we found that even if the formation of complex 3 is Ag3L52, complex 3 need more silvers to stabilize the structure in solution state, and we found that the structure of complex 2 and 3 will distorted by using the VTNMR studys.

The self-assembling process and reaction mechanism were studied by UV-Vis titration. The step-wise and overall ability constant of L、AgL、AgL2、AgL2、Ag4L2 were investigated by systematic measurement.

The results were consistent for the crystal and titration of L2 with AgPF6. Overall, double helical structure is the most stable conformation of L2 silver complex.

並列關鍵字

Supramolecule ； Silver complex ； Self-assembly ； Helicate ； Hydrazone

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