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  • 學位論文

新世代金屬分子導線的合成、結構與物理性質研究

Design and Synthesis of A New Generation Metal Wires Supported by Anthyridine Ligands

指導教授 : 彭旭明

摘要


本論文研究的目標在於透過鈴木偶合反應 ( Suzuki coupling ) 開發出新型的蒽啶衍生物配基,並利用此三氮配基合成直線型三核金屬串與雙核錯合物。 dbay (1) (dibenzanthyridine) 配基可與金屬過氯酸根鹽類反應形成雙核錯合物,M2(dbay)4(ClO4)4 (M = Fe (2), Co (3), Ni (4), Cu (5), Zn (6))。 由X-ray 單晶結構解析,所有錯合物為四個配基架橋兩個金屬形成正四價之雙核錯合物。錯合物中每個配基其中兩個氮原子鉗合一個金屬而第三個氮原子與另一個金屬配位。結構解析也分析出這五個錯合物有著相同的空間群,並且在雙核銅的錯合物有明顯的楊-泰勒效應 ( Jahn-Teller effect )。Cu-Cu距離較短為2.907(1) Å,其餘雙核錯合物金屬-金屬間的距離為3.3 Å。在鐵、鈷、鎳和銅錯合物,金屬與金屬間作用力,為反鐵磁作用力, 在鎳與銅的錯合物中,其磁交換作用常數J值分別為 -148 與 -6 cm-1。 透過自旋極化、超交換交互作用及DFT理論計算等剖析其交互作用的機制,金屬配位的幾何形狀扭曲程度較明顯而削弱了軌域正相交的作用產生了軌域混合效應,反應出比較強的反鐵磁作用。由密度泛函B3LYP方法計算出的J值與實驗值相吻合。 另外,dbay配基可與無水NiCl2/NiBr2/CuCl 金屬起始物與四苯硼鈉反應生成新一代直線型金屬串錯合物 [Ni3(dbay)4Cl2]Cl/[Ni3(Hdbay)4Br]Br/ [Ni3(dbay)4NCS]Br/[Cu3(dbay)4Cl]I 此類直線型錯合物也由單晶結構解析鑑定確認。

並列摘要


Fused and aromatic molecules are among the most attractive candidates for materials in organic thin layer devices. A pentacene analogue was prepared in only two steps by the diiodination of 2,6-diaminopyridine followed by a double Suzuki coupling with 2-formylphenyl boronic acid and spontaneous cyclization and aromatization. Dinuclear iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) complexes of 1, 13, 14-triaza-dibenz[a, j]anthracene (dibenzanthyridine = dbay, L), [M2L4](ClO4)4 (M = Fe, Co, Ni, Cu, Zn), were synthesized and their magnetic properties were studied. All complexes are dinuclear, tetracationic complexes bridged by four tridentate ligands. In a complex each L coordinates to two metal atoms with two nitrogen atoms chelating to one metal and the third nitrogen atom mono-coordinating to another metal. Crystal structure analysis indicated that the molecular structures of the five complexes are essentially the same despite various space groups and significant distortion from the Jahn-Teller effect of the copper complex. The Cu–Cu distance is 2.907(1) Å, and all other M–M distances are ca. 3.3 Å. Antiferromagnetic couplings were observed for the Fe, Co, Ni and Cu complexes. The exchange parameters were J = –148 and –6 cm–1 for Ni and Cu complexes, respectively. The mechanism was dissected by spin-polarization, superexchange coupling and DFT calculations. The seriously distorted coordination geometry of center atom might diminish the orbital orthogonality and result in orbital mixing, which leads to a strong antiferromagnetic coupling. The J value from the density functional B3LYP calculations is in good agreement with the experimentally determined value. The tridentate ligand 1,13,14-triaza-dibenz[a,j]anthracene (dibenzanthyridine = dbay) reacts with anhydrous NiCl2/NiBr2/CuCl and sodium tetraphenylborate to form a novel trinuclear complex [Ni3(dbay)4Cl2]Cl/[Ni3(Hdbay)4Br]Br/[Ni3(Hdbay)4NCS]Br/[Cu3(dbay)4Cl]I with low valent state has been structurally characterized.

並列關鍵字

Suzuki coupling Jahn-Teller effect

參考文獻


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