含苯并三唑配位基與錳、鎳金屬離子之自組裝合成、結構與性質探討

本論文分兩部分 (一) 水熱自組裝合成含1H-benzotriazole配子與nickel(II)金屬離子之配位化合1 有機配子1H-benzotriazole (HBTA)，malonic acid與硝酸鎳(Ni(NO3)2．6H2O)進行水熱自組裝合成，得到化合物[Ni9(BTA)12(NO)6] (1)。化合物1空間群為Pī，為一個含一氧化氮之九個鎳金屬中心之團簇化合物；在團簇中心鎳離子以六配位方式鍵結BTA‾配位子上的氮原子，在團簇結構外圍，六個鎳金屬中心則以四配位方式各與三個BTA‾配位子的氮原子及一個一氧化氮分子(NO)鍵結。其一氧化氮來源，推測可能來自於NO3-在酸性環境下分解而得。有趣的是，在一個含九個鎳金屬團簇結構上能夠同時具有六個一氧化氮分子，在文獻上實屬罕見。 (二) 水熱自組裝合成含1,3,5-benzenetricarboxylic acid與manganese(II)、nickel(II)之配位化合物2與3 利用1H-benzotriazole-5-carboxylic acid (H2btca)和H3BTC兩種有機配位子與錳金屬離子，以水熱法方式進行自組裝合成，得到配位化合物[Mn4(BTC)2(THF)4Cl2]n (2)；以KOH去質子化之H2btca和H3BTC配位子與鎳金屬離子以水熱法進行自組裝反應，得到配位聚合物[KNi2(C9H3O6)Cl2(H2O)2]n (3)。在合成化合物2時，所存在的H2btca 配位子並未鍵結至錳金屬離子，但卻可促進H3BTC 配子順利地與錳金屬離子鍵結，形成特別的五配位及六配位錳金屬中心之配位環境；化合物3經由X光單晶繞射解析，顯示其空間群為Pbcn。在空氣中經過一段時間化合物3會改變顏色，初步推論可能為結構發生變化，此推論在熱重損失分析圖(TGA)及粉末繞射圖(PXRD)上，也可以得到間接的證實。

關鍵字

自組裝；團簇結構；一氧化氮；磁性

並列摘要

In the first part of this thesis, self-assembly of a nickel cluster [Ni9(BTA)12(NO)6] (1) was achieved by the reaction of Ni(NO3)2．6H2O and HBTA ligand. Single-crystal X-ray diffraction analysis shows that complex 1 crystallizes in a space group Pī. Two types of coordination environment of the nickel metal centers are observed: (i) the inner three nickel atoms adopt octahedral geometry by the coordination of six nitrogen atoms from six BTA ligands; (ii) the outer six nickel metal centers adopt tetrahedral geometry, which are coordinated by three nitrogen atoms from three BTA ligands and one nitrogen atom from one NO moiety. It is noteworthy that the structure consisting of six nitrosyl groups is rare up to date. In the second part, one manganese(II) complexes, [Mn4(BTC)2(THF)4Cl2]n (2) and one nickel(II) compound [KNi2(BTC)Cl2(H2O)2]n (3), were synthesized under hydrothermal conditions. During the synthesis of complex 2, the uncoordinated H2btca ligand may plays a role in promoting the formation of 3D framework of complex 2. Complex 3 crystallizes in a space group Pbcn. This compound changed its color in the air. This might be due to the transformation of the structure upon the removing of the guest molecules. This is corroborated by the TGA and PXRD studies of compound 3.

並列關鍵字

Self-assembly ； cluster ； nitric oxide ； magnetic property

參考文獻

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含苯并三唑配位基與錳、鎳金屬離子之自組裝合成、結構與性質探討

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