含二苯乙烯三?啶衍生物之金屬錯合物：合成、光物理、光化學性質及其陽離子感測研究; Synthesis, Photophysics, Photochemistry and Binding Studies of a Series of Styrylphenyl Terpyridine Metal Complexes

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/6311

Title:	含二苯乙烯三?啶衍生物之金屬錯合物：合成、光物理、光化學性質及其陽離子感測研究;Synthesis, Photophysics, Photochemistry and Binding Studies of a Series of Styrylphenyl Terpyridine Metal Complexes
Authors:	鍾瑞庭;Ruei-ting Chung
Contributors:	化學研究所
Keywords:	感測器;三吡啶;二苯乙烯;光化學;異構化;胺基共軛效應;photochemistry;stilbene;crown ether;terpyridine;sensor;Amino-Conjugation Effect;isomerization
Date:	2007-07-09
Issue Date:	2009-09-22 10:17:23 (UTC+8)
Publisher:	國立中央大學圖書館
Abstract:	本論文利用Wittig reaction 與 Horner-Emmons reaction 方法合成二苯乙烯三吡啶系列分子，於反式-4-二苯乙烯位置銜接推電子基，藉以提升其在激發態電荷轉移之能力，並以光化學實驗分析上述行為對分子異構化的影響。我們引入「胺基共軛效應」( Amino-Conjugation Effect ) 使用單氮冠醚和二苯胺基作為推電子基，由溶劑效應的實驗結果證實，此類分子在激發態時具有很強烈的分子內電荷轉移行為，其能力大小依序為 L4 ≈ L5 > L3。透過光化學實驗結果顯示，光學異構化的行為被大幅降低，歸因於胺取代基能有效共軛的結果。我們進一步將此類分子與釕金屬和鉑金屬進行配位，利用配位基分子本身強烈的分子內電荷轉移機制與中心金屬MLCT ( metal-to-ligand charge transfer ) 的相互作用下，形成 donor-acceptor-donor 型式且具顏色改變的離子感測器。離子受體使用硫取代的單氮冠醚形成一軟鹼端，經 UV-vis 吸收光譜的滴定證實，此類感測器對於軟酸類的汞離子與銀離子具有良好的辨識能力與選擇性。另外透過模擬計算、NMR 滴定實驗和UV-vis 的吸收度改變量與離子當量之量測，發現鉑金屬錯合物的系列分子與汞離子或銀離子作用機制，並非單純的以單氮硫雜環冠醚端形成 1：1 的基本模式，而是成為 1：1、1：3 和 1：1、1：2 的特殊行為模式，由 NMR 證實是鉑金屬共同參與了反應，因而有如此特殊的行為模式。 A new series of stilbene containing 2,2’:6’,2”-terpyridine ligands has been synthesized and evaluated for their abilities for cation recognition. In order to enhance the internal charge transfer (ICT), we introduced different electron-donating subsituents such as triphenylamine and thioaza-crown. According to the results from solvent dependent studies, both L4 and L5 exhibited larger Stokes shift than L3, indicatig a stronger internal charge transfer effect in L4 and L5. Moreover, the reduced isomerization behavor in L4 and L5 is attributed to the “ Amino-Conjugation Effect ”. The ICT band of L3, L4, and L5 exhibited red shift with approximate 100 nm when coordinated to Pt(II). These metal-based chemosensors, especially PtL5Cl2, displayed stronge affinities towards Hg(II) and Ag(I) over other cations, and the changes in color was easy to be identified by naked eyes.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

Files in This Item:

File	Size	Format

社群 sharing

Loading...