鋅及銀金屬簇核心之腙基螺旋超分子

在本研究中，我們合成ㄧ系列以亞胺腙基為連結區的多牙基配位子，鍵結單元以嗒肼、萘啶和聯吡啶為主。經由單晶X-ray繞射得知配位子與Ag(I)皆能形成金屬簇螺旋錯合物。固態結構中有四銀雙金屬軸的雙螺旋錯合物，五銀不對稱三螺旋錯合物及六銀格子狀的雙螺旋錯合物。配位子與Zn(II)形成多樣化的結構，如：平面、三明治和雙螺旋結構等錯合物。利用核磁共振光譜方法，如：H-H COSY 和NOESY等方法來觀察其溶液態結構。此外藉由FAB和電灑質譜技術與元素分析確認其組成。總體而言，所合成的銀雙螺旋錯合物中，以嗒肼為鍵結單元時，銀-銀間的距離約在3.1 Å左右，其中[Ag4(Py-Me-(Pdz-Dmepzo)2)2](TfO)4錯合物，螺旋是由二股配位子沿著雙金屬軸所纏繞而成。當改用萘啶為鍵結單元時，銀-銀間的距離則縮短，約在2.7 Å左右，且銀離子間排列成格子狀形式。隨著萘啶單元的增加，目前已經開發出六銀金屬簇的結構。五銀不對稱三螺旋部份，由於結構中每股配位子的環境皆不相同，因此結構判斷上相當複雜，藉由二維和三維核磁共振光譜的COSY和NOESY等方法，可以順利的解析出溶液態結構，此為第一個完整地被報導的不對稱三螺旋型式。鋅螺旋錯合物的電子吸收光譜，具有配位子的1

關鍵字

超分子；螺旋；金屬簇；腙基

並列摘要

In this research, six series of new ligands containing hydrazone and derivative polypyridyl moiety and complexes with silver(I) and Zinc(II) to formed cluster helicates were synthesized successfully,. The crystal structures were confirmed by X-ray diffractometry. The crystal structures of these helical supramolecules were categorized in two types. The first type helical supramolecules contain one silver chain as axis in structure. The second type helical supramolecules contain two silver chains as axis in structure. Two equivalent ligands were wrapped around the metal chain axis or metal array axis in a helical conformation. The Ag-Ag distance in naphthyridine containing complexes is shorter than in pyridazine module. In naphthyridine module, the silver atom arrays in supramolecule were arranged in grid type showing stronger Ag-Ag interaction. Infinite one-dimensional arrangement of molecule by intermolecular

並列關鍵字

Hydrazone ； Metal Cluster ； Supramolecule ； Helicate ； Self-assembling ； Self-recognition

參考文獻

1 Lehn, J.-M. Supramolecular Chemistry; VCH: Weinheim, 1995.

3 Sauvage, J.-P. Transition Metals in Supramolecular Chemistry; John Wiley: New York, 1999.

4 Schneider, H.-J.; Yatsimirsky, A. Principles and Methods in Supramolecular Chemistry; John Wiley: New York, 2000.

5 Vögtle, F. Supramolecular Chemistry; John Wiley: New York, 1991.

10 Gdaniec, M.; Jankowski, W.; Milewska, M. J.; Połonski, T. Angew. Chem., Int. Ed. 2003, 42, 3903–3906.

國際替代計量

鋅及銀金屬簇核心之腙基螺旋超分子

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