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

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.