Studies of functional boron dipyrromethene derivatives.

氟硼熒二吡咯染料是一類多功能的熒光材料，並得到了廣泛的應用。本論文的目標是探索此類染料以及它的氮雜類似物作為探測重金屬離子的熒光探針，非線性光學材料和構建人工光合作用模型的潛力。 本論文報導了一系列氟硼熒二吡咯染料和它的氮雜類似物的分子設計，合成，光學性質以及在相關領域的應用。第一章簡單的概述了氟硼熒二吡咯染料的合成，光學性質和作為重金屬熒光探針和非線性光學材料的應用。然後詳細概述了氮雜氟硼熒二吡咯染料的發展，合成，光學性質，以及其在生物醫藥和材料科學領域的潛在應用。第二章報導了一個對銅和汞二價離子具有高選擇性比色性識別的近紅外熒光探針。 這個探針以雙邊苯乙烯修飾的氟硼熒二吡咯染料為螢光團，並進一步修飾兩個二（三唑）胺的識別位點。在體積比為1 比1 的乙腈水溶液中，當加入銅和汞二價離子時，這個探針的吸收和熒光波長表現出不同程度的藍移，而且這個變化可以被肉眼觀察到。這是因為分子內的電荷傳遞過程被抑制的結果。另外，通過其熒光變化的工作曲線法，銅二價離子與此探針具有2 比1 的結合比例。進一步研究表明它們表現出較大的結合常數（(6.2 ± 0.6) × 10⁹ M⁻²），是汞二價離子的結合常數的六倍。另外，除了分子內電荷傳遞的機理，光致電子轉移和熒光共振能量傳遞也是兩種常用的設計熒光探針的機理。第三章報導了兩個基於光致電子轉移和熒光共振能量傳遞的有高效選擇性的汞二價離子熒光探針。 我們使用電子吸收和熒光光譜的方法研究了他們之間的結合性能。其中一個探針在中間的位置連接了一個二（三唑）胺的結合位點，並對汞二價離子表現出很高的响應性。另一個探針進一步引入了兩個羅丹明熒光團到氟硼熒二吡咯染料上，於是當接觸到汞二價離子時，激發的氟硼熒二吡咯染料的能量將高效的傳遞到羅丹明上，從而表現出顯著的光譜的變化。第四章描述了一系列含有兩個電子供體和推拉結構的氟硼熒以及氮雜氟硼熒二吡咯染料的設計，合成，以及作為非線性光學材料的潛力。通過薗頭偶合反應，兩個對位二苯胺基苯乙炔基或對位二甲氨基苯乙炔基被連接到了該染料的2 和6 位上。線性的吸收和熒光研究表明那些化合物表現出溶劑效應。 它們在甲苯中雙光子吸收的性能通過用雙光子激發熒光光譜的方法進行了研究。另外，對於推拉電子的一系類化合物，推電子的對位二甲氨基苯乙炔基和拉電子的對位硝基苯乙炔基分別連接到了該染料的2 和6 位上。這些化合物的光學和電化學性能得到了詳細的研究。在氯仿溶液中，它們的二價非線性光學性質通過電場誘導的二次諧波的方法進行了研究，其在1907 納米的標量積μ.β在94 ×10⁻⁴⁸ 到330 × 10⁻⁴⁸ esu 之間，並隨著3 和5 位取代基的不同而變化。第五章報導了一個基於單邊苯乙烯氟硼熒二吡咯染料和富勒烯雙修飾的氮雜氟硼熒二吡咯染料的人工光合作用模型。這個三元體系的分子內光誘導的過程使用穩態的光學方法進行了研究。當激發單邊苯乙烯氟硼熒二吡咯染料部分時，這個被激發的部分會將能量傳遞給氮雜氟硼熒二吡咯染料，然後進一步的將電子傳遞給富勒烯。運用飛秒瞬態鐳射的方法，它們之間在苯睛中電子重排的速率是7.00 × 10⁸ s⁻¹，從而得到電荷分離態的壽命是1.47 納秒。作為上一個工作的拓展，第六章報導了兩個或四個甲基化環糊精修飾的氮雜氟硼熒二吡咯染料與四磺酸基卟啉和其鋅卟啉，以及兩個帶正電的單邊苯乙烯修飾的氟硼熒二吡咯染料在水中的相互作用。使用各種光學方法，我們研究了它們的結合過程以及能量或者電子的傳遞過程。最後，四磺酸基卟啉， 環糊精修飾的氮雜氟硼熒二吡咯染料，以及單邊修飾的氟硼熒二吡咯染料在水溶液中進行了自組裝。當激發卟啉時，能量高效的傳遞到氮雜氟硼熒二吡咯染料上，接著電子從單邊修飾的氟硼熒染料傳遞到氮雜氟硼熒二吡咯染料上。因此，這個多重的超分子體系是一個很好的光合作用模型。第七章和第八章分別闡述了前面幾章的實驗部分和引用文獻。論文的最後一部分附上了所有新化合物的核磁共振氫譜和碳譜圖。Boron dipyrromethenes (BODIPYs) are versatile functional materials for a wide range of applications. This research work aims to explore the potential of these compounds and their aza analogues as fluorescent probes for heavy metal ions, nonlinear optical materials, and building blocks of artificial photosynthetic models. This thesis describes the molecular design, synthesis, spectroscopic characterization, and photophysical properties of several series of BODIPYs and aza-BODIPYs, as well as their potential applications in these areas.Chapter 1 gives a brief overview of BODIPYs, focusing on their synthesis, spectroscopic properties, and applications as fluorescent probes for heavy metal ions and nonlinear optical materials. It then reviews the historical development, syntheses, and spectroscopic properties of their aza analogues. The potential applications of aza-BODIPYs in biomedicine and materials science are also discussed at the end of this chapter.In Chapter 2, a highly selective colorimetric and near-infrared fluorescent probe for Cu²⁺ and Hg²⁺ ions is reported, which is based on a distyryl BODIPY with two bis(1,2,3-triazole)amino receptors. The compound selectively binds to Cu²⁺ and Hg²⁺ ions in CH₃CN/H₂O (1:1 v/v) giving remarkably blue-shifted electronic absorption and fluorescence bands as a result of inhibition of the intramolecular charge transfer (ICT) process upon binding. The color changes can be easily seen by the naked eye. The binding stoichiometry between this probe and Cu²⁺ ion has been determined to be 1:2 by a Job’s plot of the fluorescence data with a binding constant of (6.2 ± 0.6) × 10⁹ M⁻². The corresponding value for Hg²⁺ ion is about six-fold smaller.In addition to the ICT mechanism, photoinduced electron transfer (PET) and fluorescence resonance energy transfer (FRET) are another two useful mechanisms for design of fluorescent probes. Chapter 3 reports two highly selective and sensitive BODIPY-based fluorescent probes for Hg²⁺ ion based on PET and FRET mechanisms. Their binding properties have been investigated by using electronic absorption and steady-state fluorescence spectroscopic methods. The probe with a bis(1,2,3-triazole)amino receptor at the meso position is highly responsive toward Hg²⁺ ion. By introducing two rhodamine B moieties to the BODIPY core, FRET occurs from the excited BODIPY to rhodamine B in a highly effective manner upon binding to Hg²⁺ ion, regarding to remarkable spectral changes.Chapter 4 presents a series of BODIPY and aza-BODIPY derivatives bearing a donor-π-donor or push-pull structure as nonlinear optical materials. The donor-π-donor derivatives have been prepared by connecting 4-(diphenylamino)phenylethynyl or 4-(dimethylamino)phenylethynyl moieties to the 2- and 6-positions of the π systems through Sonogashira coupling reactions. The linear optical absorption and fluorescence properties of these compounds have been found to be solvent-dependent. Their two-photon absorption properties have also been measured in toluene by two-photon fluorescence excitation method. For the push-pull series, an electron-donating 4-(dimethylamino)phenylethynyl group and an electron-withdrawing 4-nitrophenylethynyl group have been added to the 2- and 6-positions of the BODIPY core. The spectroscopic and electrochemical properties of these compounds have been studied. Their second-order nonlinear optical properties have also been examined by electric-field-induced second-harmonic generation method in CHCl₃. The values of the dot product μ.β are in the range from 94 × 10⁻⁴⁸ to 330 × 10⁻⁴⁸ esu at 1907 nm, depending on the substituents at the 3- and 5-positions.Chapter 5 describes the synthesis and characterization of an artificial photosynthetic model in which an aza-BODIPY core is covalently linked to a monostyryl BODIPY component and a fullerene (C₆₀) unit. The photoinduced intramolecular processes of this triad and the model compounds have been studied in detail by steady-state and time-resolved spectroscopic methods. Upon excitation at the monostyryl BODIPY moiety, excitation energy transfer occurs to the aza-BODIPY core, which is followed by an electron transfer to the C₆₀ unit. From the femtosecond transient absorption studies, the rate constant of charge recombination has been determined to be 7.00 × 10⁸ s⁻¹ in benzonitrile, giving a lifetime of 1.47 ns for the charge-separated state.As an extension, Chapter 6 presents related supramolecular systems in which an aza-BODIPY derivative bearing two or four permethylated β-cyclodextrin moieties binds to metal-free and zinc(II) tetrasulfonated porphyrins, as well as two cationic monostyryl BODIPYs in water. The complexation of these components has been studied by various spectroscopic methods. The resulting host-guest complexes exhibit efficient energy and/or electron transfer depending on the nature of the guests. A novel mixed array of metal-free porphyrin, aza-BODIPY, and monostyryl BODIPY has also been assembled. Upon excitation at the porphyrin unit, singlet-singlet energy transfer occurs to the aza-BODIPY core, which then obtains an electron from the monostyryl BODIPY moieties. This supramolecular hetero-array thus also serves as an artificial photosynthetic model.Chaper 7 gives the experimental details for the work described in the preceedingchapters. All the references cited herein are given in Chapter 8.¹H and ¹³C{¹H} NMR spectra of all the new compounds are given in the Appendix.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Detailed summary in vernacular field only.Shi, Wenjing.Thesis (Ph.D.)--Chinese University of Hong Kong, 2013.Includes bibliographical references (leaves 204-220).Abstracts also in Chinese.Table of Contents --- p.IAcknowledgment --- p.VIIAbstract --- p.IXAbstract (in Chinese) --- p.XIIIAbbreviations --- p.XVList of Figures --- p.XXIList of Tables --- p.XXXIIList of Schemes --- p.XXXIVPublication Related to This Thesis --- p.XXXVIChapter Chapter 1 --- IntroductionChapter 1.1 --- General --- p.1Chapter 1.2 --- Synthesis, Reactivity, and Spectroscopic Properties of BODIPYs --- p.2Chapter 1.2.1 --- Synthesis of BODIPYs --- p.2Chapter 1.2.2 --- Reactivity of BODIPYs --- p.5Chapter 1.2.3 --- Spectroscopic Properties of Selected BODIPYs --- p.6Chapter 1.3 --- Applications of BODIPYs --- p.9Chapter 1.3.1 --- BODIPYs as Fluorescent Probes for Heavy Metal Ions --- p.9Chapter 1.3.2 --- BODIPYs as Two-Photon Absorbing Materials --- p.14Chapter 1.3.2.1 --- General for Two-Photon Absorption --- p.14Chapter 1.3.2.2 --- Selected Examples of TPA Materials --- p.15Chapter 1.4 --- Aza-BODIPYs: Aza Analogues of BODIPYs --- p.18Chapter 1.4.1 --- General --- p.18Chapter 1.4.2 --- Synthesis and Reactivity of Aza-BODIPYs --- p.18Chapter 1.4.3 --- Spectroscopic Properties of Aza-BODIPYs --- p.21Chapter 1.4.4 --- Applications of Aza-BODIPYs --- p.29Chapter 1.4.4.1 --- Aza-BODIPYs as Artificial Photosynthetic Models --- p.29Chapter 1.4.4.2 --- Aza-BODIPYs as Fluorescent Probes --- p.33Chapter 1.4.4.3 --- Aza-BODIPYs as Photosensitizers and Imaging Probes --- p.37Chapter 1.4.4.4 --- Other Applications --- p.39Chapter 1.5 --- Objectives of this Study --- p.41Chapter Chapter 2 --- A Highly Selective Colorimetric and Fluorescent Probe for Cu²⁺ and Hg²⁺ Ions Based on a Distyryl BODIPY with Two Bis(1,2,3-triazole)amino ReceptorsChapter 2.1 --- Introduction --- p.42Chapter 2.2 --- Results and Discussion --- p.43Chapter 2.2.1 --- Synthesis and Characterization --- p.43Chapter 2.2.2 --- Metal Sensing Properties --- p.46Chapter 2.2.3 --- Binding Properties --- p.48Chapter 2.2.3.1 --- Binding Properties of 2.10 with Cu²⁺ Ion --- p.48Chapter 2.2.3.2 --- Binding Properties of 2.10 with Hg²⁺ Ion --- p.52Chapter 2.3 --- Conclusion --- p.55Chapter Chapter 3 --- Detection of Hg²⁺ Ion with BODIPY-Based Fluorescent Probes Substituted with a Bis(1,2,3-triazole)amino ReceptorChapter 3.1 --- Introduction --- p.56Chapter 3.2 --- Results and Discussion --- p.57Chapter 3.2.1 --- Molecular Design, Synthesis, and Characterization --- p.58Chapter 3.2.2 --- Metal Binding Properties of 3.6 --- p.61Chapter 3.2.3 --- Metal Binding Properties of 3.7 --- p.66Chapter 3.2.4 --- Fluorescence Resonance Energy Transfer in 3.7 --- p.72Chapter 3.3 --- Conclusion --- p.73Chapter Chapter 4 --- Synthesis and Nonlinear Optical Properties of BODIPY and Aza-BODIPY DerivativesChapter 4.1 --- Introduction --- p.74Chapter 4.2 --- Results and Discussion --- p.75Chapter 4.2.1 --- Synthesis of D-π-D BODIPY and Aza-BODIPY Derivatives --- p.75Chapter 4.2.2 --- Synthesis of Push-Pull BODIPY Derivatives --- p.81Chapter 4.2.3 --- Linear Electronic Absorption and Fluorescence Properties of D-π-D BODIPY and Aza-BODIPY Derivatives --- p.84Chapter 4.2.4 --- Electrochemical Properties of D-π-D BODIPY Derivatives --- p.88Chapter 4.2.5 --- Two-Photon Absorption Properties of D-π-D BODIPY and Aza-BODIPY Derivatives --- p.90Chapter 4.2.6 --- Linear Electronic Absorption and Fluorescence Properties of Push-Pull BODIPY Derivatives --- p.93Chapter 4.2.7 --- Electrochemical Properties of Push-Pull BODIPY Derivatives --- p.96Chapter 4.2.8 --- Second-Order Nonlinear Optical Properties of Push-Pull BODIPY Derivatives --- p.97Chapter 4.3 --- Conclusion --- p.99Chapter Chapter 5 --- Photosynthetic Antenna-Reaction Center Mimicry with a Covalently Linked Monostyryl Boron Dipyrromethene-Aza Boron Dipyrromethene-C₆₀ TriadChapter 5.1 --- Introduction --- p.101Chapter 5.2 --- Results and Discussion --- p.103Chapter 5.2.1 --- Synthesis --- p.103Chapter 5.2.2 --- Steady-State Electronic Absorption and Fluorescence Properties --- p.105Chapter 5.2.3 --- Electrochemical Properties and Energy Levels --- p.109Chapter 5.2.4 --- Transient Absorption Studies --- p.112Chapter 5.2.4.1 --- Femtosecond Transient Absorption Studies --- p.112Chapter 5.2.4.2 --- Nanosecond Transient Absorption Studies --- p.117Chapter 5.2.5 --- Energy-Level Diagrams --- p.119Chapter 5.3 --- Conclusion --- p.121Chapter Chapter 6 --- Formation and Photoinduced Processes of the Host-Guest Complexes of β-Cyclodextrin-Conjugated Aza-BODIPYs with Tetrasulfonated Porphyrins and Monostyryl BODIPYsChapter 6.1 --- Introduction --- p.122Chapter 6.2 --- Results and Discussion --- p.123Chapter 6.2.1 --- Synthesis and Characterization --- p.123Chapter 6.2.2 --- Host-Guest Complexes of 6.3 with Tetrasulfonated Porphyrins --- p.131Chapter 6.2.3 --- Host-Guest Complexes of 6.7 with Tetrasulfonated Porphyrins --- p.141Chapter 6.2.4 --- Host-Guest Complexes of 6.7 with Monostyryl BODIPYs --- p.146Chapter 6.2.5 --- Host-Guest Complexes of 6.7 with Tetrasulfonated Porphyrins and Monostyryl BODIPYs --- p.154Chapter 6.3 --- Conclusion --- p.159Chapter Chapter 7 --- Experimental SectionChapter 7.1 --- General --- p.160Chapter 7.2 --- Experiments in Chapter 2 --- p.162Chapter 7.2.1 --- Synthesis --- p.162Chapter 7.2.2 --- Absorption and Fluorescence Studies --- p.164Chapter 7.2.3 --- Determination of Binding Constants (K) --- p.165Chapter 7.3 --- Experiments in Chapter 3 --- p.165Chapter 7.3.1 --- Synthesis --- p.165Chapter 7.3.2 --- Absorption and Fluorescence Studies --- p.169Chapter 7.3.3 --- Determination of Binding Constants (K) --- p.169Chapter 7.4 --- Experiments in Chapter 4 --- p.170Chapter 7.4.1 --- Synthesis --- p.170Chapter 7.4.2 --- Electrochemical Measurements --- p.188Chapter 7.4.3 --- NLO Measurements --- p.188Chapter 7.5 --- Experiments in Chapter 5 --- p.190Chapter 7.5.1 --- Synthesis --- p.190Chapter 7.5.2 --- Electrochemical Measurements --- p.196Chapter 7.5.3 --- Time-Resolved Transient Absorption Measurements --- p.196Chapter 7.6 --- Experiments in Chapter 6 --- p.198Chapter 7.6.1 --- Synthesis --- p.198Chapter 7.6.2 --- Determination of Binding Constants (K) --- p.201Chapter 7.6.3 --- Molecular Dynamic Simulation --- p.202Chapter 7.6.4 --- Electrochemical Measurements --- p.203Chapter Chapter 8 --- References --- p.204Appendix --- p.22