含Perylene Bisimide and Platinum 錯合物核心並以氫健自組裝 Triarylamine 樹枝狀分子做為金屬離子感測及能量轉移新穎材料之合成與研究

Abstract

本文的主要目的是合成新型化學敏感材料的金屬離子選擇性檢測，並研究電子/能量轉移中氫鍵的新型三芳胺樹枝狀苝雙酰亞胺和鉑配合物的核心組件。我們在引進的論文中所描述的幾個化學傳感機制和超分子相互作用的概念。許多傳感器探頭對Cu2+和Fe3 +，Zn2 +的，Al3+和Hg2+ 離子。在此，我們對Cu2 + “關閉”傳感器開發的新型三芳胺樹枝狀。此外，芘和蒽的席夫鹼衍生物，Cu2+和Fe3 + “導通”的傳感器，分別和簡單的吡啶 - salicylimine探頭對Zn2+和Al3 + 為不同的傳感器。此外，對比前一報告，比色法檢測Hg2+和半胱氨酸通過J-苝雙酰亞胺衍生物的聚合和分解機制是很好的證明。除了傳感器研究，我們也研究了自組裝和中氫鍵的三芳基胺樹枝狀苝雙酰亞胺和鉑複雜的核心組件之電子/能量轉移。 在第二章中，兩個新的高度可溶性的三芳基胺的樹枝狀TPAD1和TPAD2與N4，N6-二丁基-1,3,5 - 三嗪-4,6 - 二胺探頭透過正常的合成路線合成。將這兩個的樹枝狀（TPAD1和TPAD2）形成氫鍵予體 - 受體供體（DAD），TPAD1-的PBI-TPAD1和TPAD2-PBI-TPAD2 3,4,9,10 - 苝四羧酸二酰亞胺衍生物（PBI）。存在多個H-在溶液狀態下透過1H NMR滴定和紅外光譜的研究。 J-聚集和兩個樹枝狀所提供的電子/能量轉移，驗證由PBI和超分子三合會的粒子尺寸，透過X-射線衍射（XRD）分析計算的UV / Vis和PL滴定。同樣的，這兩個樹枝狀顯示，比起其他的19干擾金屬離子，對Cu2 + 更有選擇性，這是證明單，雙金屬系統透過UV / VIS和PL 驗證。最大樹枝狀檢測極限為20 ppm的Cu2 +離子熒光滴定，並在1:2化學計量學的複合物由兩種樹枝狀形成（TPAD1，對Cu2 + 和TPAD2，對Cu2 +）分別計算UV /可見吸收光譜滴定法。更重要的是，1,3,5 - 三嗪-4,6 - 二胺探頭兩個樹枝狀的結合機制，以及其特徵在於透過1H和13C NMR滴定（[D8]十二烷基硫酸鈉：D 2 O = 2:1體積）由熒光透過依次添加金屬離子和PMDTA的其表現是可逆性。 在第三章中，新穎性的蒽類芘和雙功能希夫基地衍生物P1和A1進行合成，透過反應和熒光分別對Cu2 +和Fe3 +離子的聚集引起的釋放（獨立實體）傳感器。 P1在CH3CN和A1焦磷酸鉀中說明了熒光轉式傳感器針對Cu2 +和Fe3 + 離子，分別通過螯合熒光增強（CHEF）透過準分子（P1-P1 * A1-A1 *）的形成。 2:1的化學計量傳感器複合物（P1 + Cu2 +和A1 + Fe3 +），紫外 - 可見吸收滴定的基礎上計算的工作圖。此外，傳感器的複合物的結合位點（P1 + Cu2 +和A1 +Fe3 +) 以及從1H NMR滴定建立和透過依次添加金屬離子和PMDTA。由熒光可逆性方法的檢出限（檢測限），並結合常數（KA）值P1 + Cu2 + 和A1 + Fe3 + 標準偏差和線性擬合和熒光結合等溫線，分別對傳感器響應進行了計算。更重要的是，P1 + Cu2 + 和A1 + Fe3 +的傳感器被發現是活躍的在寬範圍內的pH值（分別為1-14和2-14）。 此外，解決隨著增強的量子產率（Φ）和時間的時間效應的光致發光（TRPL）衰減常數（τ）對傳感器響應進行了研究。同樣的，CH3 CN 中的P1和A1的THF表明通過增加的含水介質中的濃度從0％到90％的經認證的獨立實體，與改變的熒光峰移（分別為紅色和藍色的變化）。以及τ值的增強，其中Φ值0.506和0.567（630 和101的增強功能），乙腈：水（20:80）而A1在THF：H2O（40:60）分別為P1 。

在第四章中，簡單的吡啶salicylimine衍生工具（F1，F2和F3）熒光“開啟的”感應器針對不同的檢測的Zn2+，Al3+的OH-在混合水介質CH3CN/H2O的離子與第一次報告。比6/4和3/7（pH = 7和25°C） 通過內電荷轉移（ICT），螯合熒光增強（CHEF），和去質子化機制。 F1和F2顯示多樣化的開啟傳感應用以Zn2 +，Al3+的和OH-離子，但F3表現出的熒光的導通的感測到鋁+和OH-離子在CH3CN/H2O（6/4）。F1 +鋅+ F2 + Zn2+ 絡合物顯示對Zn2 +的可逆性和比例的位移與乙二胺四乙酸（EDTA）和Al3+ 離子，分別在CH3CN/H2O（6/4）。另一方面，F1，F2和F3在CH3CN/H2O （3/7表明靈敏度僅Al3 + 離子，但可以忽略不計的OH - 離子的選擇性。 計算公式為1:1的化學計量所有的傳感器配合工作的基礎上UV / Vis和PL滴定的陰謀。 所有的傳感器材料的複合物的形成和結合位點，以及其特徵在於由1H，13C-NMR，和質譜（FAB）頻譜分析。檢測限（檢測限）計算標準偏差和線性擬合計算。結合常數值的傳感器配合物的熒光結合等溫線進行了評價。時間分辨熒光（TRPL）的研究熒光衰減常數（τ）值進行估計。在本文中對傳感器響應的時間、溫度、pH值和溶劑濃度的影響進行全面研究。 在第5章中，選擇性肉眼和熒光傳感器響應的1,6,7,12 - 四（4 - 叔丁基苯氧基）苝3 ,4:9,10 - 四羧酸雙酰亞胺（PBI）衍生物第一個報導時間對Hg2 +離子的離子和半胱氨酸（Cys）的透過J-聚集及解聚機制。 J-聚集和聚集PBI誘導解離的Hg2 +和Cys建立由UV-Vis/PL和1H NMR滴定。 1:1的化學計量PBI-Hg2 +和Cys-Hg2 + / PBI合奏的鑑定工作圖，根據他們的紫外 - 可見吸收光譜變化。線性複雜地層的PBI- Hg2 +的組成透過FT-IR和1H NMR譜研究證實，另外五甲基二亞乙基三胺（PMDTA）很好的支持其可逆性質。Hg2 + cooperativities + PBI- Hg2 +和Cys和Cys-Hg2 + / PBI的熒光結合曲線可從圖上證明。 36.6和91.3計算的檢測出Hg2 +和Cys，分別透過線性模擬的標準偏差和Volmer方程（KSV）的不變和相對的熒光強度的變化。此外，傳感器性能的PBI有很好的KSV、pH值、時間分辨熒光光譜（TRPL）和時間影響的研究。 在第六章中，兩種新型超分子氫鍵四分[PTC(TPAD1)3和PTC（TPAD2)3]，包括中央鉑配合物（PTC）受體與氫鍵受體單位和三苯胺樹枝狀（TPAD1和TPAD2）作為予體者成功地合成透過合成路線與改進在普通有機溶劑中的溶解度。氫鍵的存在解決了固態鑑定透過1H NMR滴定和紅外光譜的研究。電子/能量轉移以及自組裝的超分子四分體，完成了由UV-Vis和PL滴定法和原子力顯微鏡研究。 因此，結論是開發新型化學敏感材料的金屬離子的選擇性檢測。修正了敏感性圖案相對於機制和取代基效應進行了討論。此外，電子/能量轉移在苝雙酰亞胺衍生物和鉑配位核心的三芳基胺樹枝狀聚合物與氫粘合組件進行詳細說明。

The prime objective of this dissertation is to synthesize novel chemosensor materials for selective detection of metal ions and to study the electron/energy transfers in hydrogen bonded assemblies of novel triarylamine dendrimers with perylene bisimide and platinum complex cores. In the introduction of the thesis we have described about several chemosensing mechanisms and the concepts of supramolecular interactions. Many sensor probes were reported for Cu2+, Fe3+, Zn2+, Al3+ and Hg2+ ions. Herein, we have developed two novel triarylamine dendrimers as Cu2+ “Turn-Off” sensors. Furthermore, Pyrene and Anthracene based Schiff base derivatives as Cu2+ and Fe3+ “Turn-On” sensors, respectively, and simple pyridyl-salicylimine probe was reported as distinct sensors for Zn2+ and Al3+ ions. In addition, contrast to the previous report, colorimetric detection of Hg2+ and Cys via J-aggregation and disaggregation mechanisms of a perylene bisimide derivative was well demonstrated. Apart from the sensor studies, we also studied the self-assembly and electron/energy transfers involved in hydrogen bonded assemblies of those triarylamine dendrimers with perylene bisimide and platinum complex cores. In chapter two, two novel highly soluble triarylamine dendrimers TPAD1 and TPAD2 with N4,N6-dibutyl-1,3,5-triazine-4,6-diamine probe were synthesized via normal synthetic routes. Both dendrimers (TPAD1 and TPAD2) forms H-bonded donor-acceptor-donor (D-A-D) supramolecular triads TPAD1-PBI-TPAD1 and TPAD2-PBI-TPAD2 with 3,4,9,10-perylene tetra carboxylic diimide derivative (PBI). The presence of multiple H-bonds in solution state was elucidated by 1H NMR titrations and IR spectral studies. J-aggregations and electron/energy transfers provided by both dendrimers were verified by UV/Vis and PL titrations with PBI and the particle sizes of supramolecular triads were calculated by X-ray diffraction (XRD) analysis. Similarly, both dendrimers also showed sensitivities towards Cu2+ in comparison with 19 interfering metal ions, which were evidenced via UV/Vis and PL titrations in both single and dual metal systems. The maximum detection limit of Cu2+ ions was determined as 20 ppm from fluorescence titrations for both dendrimers, and the 1:2 stoichiometry of the complexes formed by both dendrimers (TPAD1-Cu2+ and TPAD2-Cu2+) were calculated by Job plots based on UV/Vis absorption titrations. More importantly, the binding mechanism of 1,3,5-triazine-4,6-diamine probe of both dendrimers was well characterized by 1H and 13C NMR titrations ([D8]THF:D2O = 2:1 in vol.) and supported by the fluorescence reversibility by adding metal ions and PMDTA sequentially. In chapter three, novel pyrene- and anthracene-based bifunctional schiff base derivatives P1 and A1 were synthesized via one-pot reaction and utilized as fluorescence turn-on sensors towards Cu2+ and Fe3+ ions, respectively, and for aggregation induced emissions (AIEs). P1 in CH3CN and A1 in THF illustrated the fluorescence turn-on sensors towards Cu2+ and Fe3+ ions, respectively, via chelation enhanced fluorescence (CHEF) through excimer (P1-P1* and A1-A1*) formations. The 2:1 stoichiometry of sensor complexes (P1+Cu2+ and A1+Fe3+) were calculated from job plots based on UV-Vis absorption titrations. In addition, the binding sites of sensor complexes (P1+Cu2+ and A1+Fe3+) were well established from the 1H NMR titrations and supported by the fluorescence reversibility by adding metal ions and PMDTA sequentially. The detection limits (LODs) and the association constant (Ka) values of P1+Cu2+ and A1+Fe3+ sensor responses were calculated by standard deviations and linear fittings and from their fluorescence binding isotherms, respectively. More importantly, P1+Cu2+ and A1+Fe3+ sensors were found to be active in wide ranges of pHs (1-14 and 2-14, respectively). Moreover, the time effect along with the enhancements of quantum yield (Φ) and time resolved photoluminescence (TRPL) decay constant (τ) towards sensor responses were investigated. Similarly, P1 in CH3CN and A1 in THF showed AIEs by increasing the aqueous media concentration from 0% to 90%, with altered fluorescence peak shifts (red and blue shifts, respectively). As well as τ value enhancements, the Φ values of 0.506 and 0.567 (with 630- and 101-fold enhancements) were acquired for P1 in CH3CN:H2O (20:80) and A1 in THF:H2O (40:60), respectively. In chapter four, simple pyridyl-salicylimine derivatives (F1, F2 and F3) are reported for the first time as fluorescence “turn-on” sensors for distinct detections of Zn2+, Al3+ and OH- ions in mixed-aqueous media CH3CN/H2O with vol. ratios of 6/4 and 3/7 (at pH = 7 and 25°C) via internal charge transfer (ICT), chelation enhanced fluorescence (CHEF), and deprotonation mechanisms. F1 and F2 showed diverse turn-on sensing applications to Zn2+, Al3+ and OH- ions, but F3 exhibited the fluorescence turn-on sensing to Al3+ and OH- ions in CH3CN/H2O (6/4). F1+Zn2+ and F2+Zn2+ complexes revealed the reversibilities and ratiometric displacements of Zn2+ with ethylene diamine tetra acetic acid (EDTA) and Al3+ ions, respectively, in CH3CN/H2O (6/4). On the other hand, F1, F2 and F3 in CH3CN/H2O (3/7) showed sensitivities only to Al3+ ions but negligible selectivities to OH- ions. Stoichiometry of all sensor complexes were calculated as 1:1 by job’s plots based on UV/Vis and PL titrations. The complex formation and binding sites of all sensor materials were well characterized by 1H, 13C-NMR, and mass (FAB) spectral analysis. Detection limits (LODs) were calculated from standard deviations and linear fitting calculations. The association constant (log Ka) values of sensor complexes were evaluated from the fluorescence binding isotherms. The fluorescence decay constant (τ) values were estimated from time resolved fluorescence (TRPL) studies. Time, temperature, pH and solvent concentration effects towards sensor responses were fully investigated in this report. In chapter five, Selective naked eye and fluorescent sensor responses of 1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide (PBI) derivative was reported for the first time towards Hg2+ ions and Cysteine (Cys) via J-aggregation and deaggregation mechanisms. The J-aggregation and dissociation of aggregation of PBI induced by Hg2+ and Cys were well established by UV-Vis/PL and 1H NMR titrations. The 1:1 stoichiometry of PBI-Hg2+ and Cys-Hg2+/PBI ensembles were elucidated from the jobs plots based on their UV-Vis spectral changes. The linear complex formation by PBI-Hg2+ ensemble was confirmed through FT-IR and 1H NMR spectral studies and well supported by its reversible nature upon addition of penta methyl diethylene triamine (PMDTA). The positive degree of cooperativities of Hg2+ and Cys in PBI-Hg2+ and Cys-Hg2+/PBI ensembles were evidenced from the hill plots based on their fluorescence binding isotherms. The detection limits of Hg2+ ions and Cys were calculated as 36.6 and 91.3 nM, respectively, by standard deviation and linear fittings of their stern-Volmer (KSV) constant and relative fluorescence intensity changes, respectively. Furthermore, the sensor properties provided by PBI was well supported by KSV, pH, time resolved photoluminescence (TRPL) spectra and time effect investigations. In chapter six, Two novel supramolecular Hydrogen bonded tetrads [PtC(TPAD1)3 and PtC(TPAD2)3] containing central platinum complex (PtC) acceptor with hydrogen bond acceptor pendant unit and triarylamine dendrimers (TPAD1 and TPAD2) as donors were synthesized successfully through affordable synthetic routes with improved solubility in common organic solvents. The presence of hydrogen bonds in solution and solid state were elucidated by 1H NMR titrations and IR spectral studies, respectively. The electron/energy transfers as well as the sef-assemblies of supramolecular tetrads were established by UV-Vis and PL titrations and AFM studies. Thus in conclusion, novel chemosensor materials were developed for selective detections of metal ions. Amendments of sensitivity pattern with respect to mechanisms and substituent effects were discussed. Furthermore, the electron/energy transfer in hydrogen bonded assemblies of triarylamine dendrimers with perylene bisimide derivative and platinum complex core were described in detail.