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    Title: 含氮橋基雙雜菲衍生物 : 合成及金屬感測器性質研究
    Other Titles: Studies of bis(1,10-Phenanthrolin-2-yl)amine derivatives : synthesis and metal ion sensing
    Authors: 蔡孟宏;Tsai, Meng-Hung
    Contributors: 淡江大學化學學系碩士班
    王文竹;Wang, Wen-Jwu
    Keywords: 雙核錯合物;電荷轉移躍遷;Oxo bridge dinucear complex;Oxo to metal CT state
    Date: 2013
    Issue Date: 2014-01-23 13:45:21 (UTC+8)
    Abstract: 一系列1,10-二氮雜菲(1,10-phenanthroline)架構的衍生物被合成,得到三個新的配位子NpDPA、EtDPA、及AlDPA,分別以L1、L2、及L3代號稱之。L1是在bis(1,10-Phenanthrolin-2-yl)amine的架橋氮原子上,接上一個光學活性的亞甲基萘分子團,並將其運用在化學螢光感測器上,是研究的重點。

    NpDPA的酸鹼性質是以滴定的電子吸收光譜變化,計算得到H2NpDPA2+的pKa1 = 2.93及HNpDPA+的pKa2 = 4.79。L1與硝酸鐵反應,得到含Fe-O-Fe的雙核鐵錯合物 [(Fe(NpDPA)(H2O))2O](NO3)4 (2),且經x-ray繞射取得單晶結構,分子間的堆疊為π-π作用力。在光譜研究,電子吸收光譜顯示錯合物2,因錯合物為Fe-O-Fe結構,在光譜中有兩個特別的吸收峰範圍為320-325 nm與 360-380 nm,此吸收峰為O → Fe電荷轉移躍遷。發射光譜中,錯合物2 在547 nm有放射峰,此放射峰來自於O → Fe電荷轉移躍遷的放光行為。而錯合物3 ( 3 = [Cr2O(NpDPA)2(H2O)2](Cl)4 )與錯合物2光譜一致,具有特異的發光性質。NpDPA與金屬配位後產生光誘導電子轉移效應(Photoinduced Electron Transfer , PET),使配位子螢光淬滅(quenching),主要是亞甲基萘為一個推電子基,增強橋基氮孤對電子的分子內電荷轉移。

    金屬錯合物的發射光譜顯示三種金屬為Cr(III)、Fe(III)、Au(III)有相同的放光行為,經加入KI後,將突顯Cr(III)放光行為且化學螢光感測對Cr(III)具有專一性。這些錯合物的特異性,將在本論文仔細探討及研究。
    A series of new bis(1,10-Phenanthrolin-2-yl)amine (HDPA) derivatives have been synthesized (L1 = NpDPA、L2 = EtDPA、L3 = AlDPA). The L1 incorporate a naphthalenylmethylene group on the bridge nitrogen atom of HDPA as a new fluorophore. This study focused on the specific luminescence properties of L1. The UV-Vis spectra of L1 as a function of pH gave acidity constants of H2NpDPA2+ (pKa1 = 2.93) and HNpDPA+ (pKa2 = 4.79). Coordination of L1 with iron(III) nitrate yielded the corresponding [Fe2O(NpDPA)2(H2O)2](NO3)4 complex 2. The x-ray crystallography revealed the oxo-bridged dinuclear structure of complex 2. The Fe-O-Fe bridges have been reported to exhibit electronic transition at 320-325 nm and 360-380 nm which was assigned to charge transfer absorption. The fluorescence at lower energy wavelength 547 nm (ex = 370nm) was observed. This emission was attributed to an Oxo→Fe(III) charge transfer states. The Cr(III) ion exhibited similar spectroscopic properties as the Fe(III) complex 2. The photophysical studies concluded that the luminescence quenching in the L1 is due to the photo-induced electron transfer (PET) from the naphthalenylmethylene group, which is an electron releasing group that increased the internal charge transfer (ICT) resulting from the bridged nitrogen atom to phenanthroline. The specific fluorescence of L1 at 547 nm when associated with Cr(III) and Fe(III) ions shows selective metal ion sensing ability. The emission was sensitive with Cr(III) with no or weak interference by other cations.
    Appears in Collections:[Graduate Institute & Department of Chemistry] Thesis

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