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    題名: 雙亞胺配位銅(I)、銀(I)及釕錯合物之合成與性質
    其他題名: Syntheses and characterizations of copper(I), Ag(I) and Ru complexes with α-diimine ligands
    作者: 林建合;Lin, Chien-ho
    貢獻者: 淡江大學化學學系碩士班
    王文竹;Wang, Wen-jwu
    關鍵詞: 雙亞胺配位子;α-diimine
    日期: 2005
    上傳時間: 2010-01-11 02:49:11 (UTC+8)
    摘要: 近幾年來,含有雙亞胺基的配位子在光化學及超分子自我組裝領域已經被廣泛地研究,因此在此論文中,藉由L1配位子( 3,5-di(2’-pyridyl)-4-amino-1,2,4-triazole )及L3配位子( 3,5-di(2’-pyridyl)-1,2,4-oxadiazole )經由縮合反應而合成一系列具有五圓環架橋基的配位子,隨後部份的配位子分別與釕、銅(I)及銀(I)金屬合成出四個系列的錯合物,如[Ru(L)(bpy)2](PF6)2、 [Ag(L)(PPh3)2](ClO4) 、[Cu(L)(PPh3)I]及[Ag(L)]n(ClO4)n。

    在[Ru(L)(bpy)2](PF6)2系列中,利用吸收光譜得知在可見光區約445nm左右處為MLCT的吸收峰,而發射光譜顯示在長波長約600 ~660nm間為磷光放射的放射峰,在[Ru(L3)(bpy)2](PF6)2循環伏安光譜中,從氧化還原電位得知RuII / RuIII位於E= +1.345V,bpy / bpy-位於E= +1.345、-1.235V,而L / L-位於-1.865及-2.16V,最後藉由吸收光譜及循環伏安光譜的探討,推得由bpy佔據最低π*軌域能階。

    在[Cu(L)(PPh3)I]系列中,從吸收光譜得知在可見光區約350 ~ 545nm間為MLCT的吸收峰,而發射光譜顯示在長波長約600 ~640nm間為磷光放射的放射峰,最後在[Cu(L1)(PPh3)I]循環伏安光譜得知CuI / CuII及CuI / Cu0的氧化還原分別位於E= +0.685及-0.545V,而這樣數據是符合典型銅(I)錯合物在電化學上的表現。

    在[Ag(L)(PPh3)2] ](ClO4) 及[Ag(L)]n(ClO4)n系列中,藉由吸收光譜得知在可見光區並沒有任何的MLCT吸收峰,而發射光譜顯示錯合物的發光性質與配位子相同。

    在[Ag(L)]n(ClO4)n系列中,藉由X-ray晶體繞射法解出的晶體結構顯示,錯合物是由配位子與銀(I)離子在1:1比例情況下形成一維結構的聚合物,並且銀跟銀離子間沒有交互作用力,至於在兩面角數據得知Ag(I)金屬中心為扭曲的幾何圖形,而晶體推疊數據顯示分子內有弱的π-π作用力存在,最後這一類的聚合物在超分子排列分類為拉鏈型(zipper)的結構。
    The use of the diimine moiety as a part of ligand systems has gained considerable attention in recent years. This is mainly because of the fact that these ligands have the good characteristics of conjugat π electronic system and lowπ* orbital. Further, the investigations on the chemical and physical behavior of ruthenium(II) complexes with the polydendate chelating ligands have attracted much attention. As a consequence of their unique combination of ground- and excited-state properties, this class of coordination complexes has played an important role in the devolpment of chemistry, such as photochemistry, photophysical, photocatalysis, electrochemistry, chemiluminescence, electrochemiluminescence, and supramolecular photochemistry. The main purpose of this study is to synthesze and characterize a series of novel diimine ligands, and their Ru(II), Ag(I) and Cu(I) complexes, [Ru(L)(bpy)2](PF6)2, [Ag(L)(PPh3)2] (ClO4), [Cu(L)(PPh3)I] and [Ag(L)]n(ClO4)n .

    The absorption spectra of the Ru(II) series complexes show intense ligand-centered(LC) bands in the UV region and broad metal-to-ligand charge-transfer(MLCT) bands at lower bands, about 445nm. All the Ru(II) complexes exhibit intense photoluminescence, which has been attributed to MLCT triplet emission. The maximum emission wavelengths at room temperature in the range of 600 ~660 nm. The cyclic voltammetry was measured, showing a metal-centered RuII / RuIII oxidation with potentials at 1.345 V, as well as two reversible reduction waves with potentials at -1.235 V and -2.16 V, attributed to bpy / bpy- and L / L- respectively. According to the result above, presuming the lowestπ* orbital is occupied by bpy .

    In the series complexes of Cu(I), the The absorption spectra show MLCT bands ranging from 350 nm to 545 nm, and the maximum emission wavelengths at room temperature in the range of 600 ~640 nm. The cyclic voltammetry show the CuI / CuII oxidation and CuI / Cu0 reduction with the potentials at 0.685 V and –0.545 V respectively. The electrochemistry behavior correspond with the typical Cu(I) property of the literature .

    In the complexes of [Ag(L)(PPh3)2] ](ClO4) and [Ag(L)]n(ClO4)n, all the photophysical properties are similar to their ligands’ .

    The complex, [Ag(L)]n(ClO4)n is prepared in a 1:1 ligand-to-metal molar ratio and structurally characterized by single-crystal X-ray analysis, showing one-dimensional coordination polymers. The Ag(I) centers exhibit a distorted tetrahedral configuration, there are not obvious interactions with the adjacent Ag(I) units, but exist weak π•••π stacking interactions in the crystal packing. The coordination polymers are characterized as zipper structure .
    顯示於類別:[化學學系暨研究所] 學位論文

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