周必泰Chou, Pi-Tai臺灣大學:化學研究所林奕志Lin, Yi-ChihYi-ChihLin2010-06-302018-07-102010-06-302018-07-102009U0001-0707200922005300http://ntur.lib.ntu.edu.tw//handle/246246/187506z-scan量測技術(Chapter 1)主要是將一道雷射光沿著樣品移動方向(z軸)聚焦並同時偵測光強度的改變，通常光強度的變化會是樣品在z軸位置的函數。假設如果在偵測器前面加上一個窄孔(我們通常稱呼為閉孔式裝置)，此時所偵測到的光強度變化會與光強度所造成的物質折射率改變相關，而物質折射率改變的會導致雷射光在焦點附近重新自聚焦或是自發散，這種現象主要是由三階非線性效應所引起。相對地，若偵測器前未加任何的孔並將所有的光都收集起來(我們通常稱呼為開孔式裝置)，此時所偵測到穿透光的強度變化會反應因光強度變化所造成的物質雙光子吸收。由以上的實驗裝置，我們可以簡單、快速且精準地測量物質本身的三階非線性效應及其物理量。 在本論文中，我主要是研究一系列金(I)-銅(I)、金(I)-銀(I)與銀(I)-銅(I)之異種金屬錯合物的光物理性質，並且利用自己所架設的z-scan量測技術測量其雙光子吸收特性(Chapter 3-7)。這些異種金屬錯合物主要都是經由自組裝結合而成，其光物理性質主要是具有很強的磷光放光性質，原因主要是因為metal-to-ligand charge transfer包含了中心的重金屬原子(如金、銀與銅)用以增強spin-orbit coupling，並造成強的磷光放光。更重要的是在有氧的情形下，這些磷光不具有oxygen quenching的效應，主要原因是在外圍的取代基太過於龐大，可以有效的保護電子在三重激發態時，不會被氧氣經由碰撞的形式代謝掉能量。同時間，我們也量測這些錯合物的雙光子吸收，結果顯示這些樣品不但具有強的磷光同時也具有較大的雙光子吸收係數(與一般的染料比較)。結合磷光與雙光子吸收這兩種性質，可提供這些樣品應用於時間解析影像與雙光子顯微技術的機會。The z-scan technique involves moving a sample along the path of a focused laser beam and measuring the light intensity at the detector as a function of its position along this z-axis (Chapter 1). If the detector has a narrow aperture (as in the so called “closed-aperture” setup), then the output is sensitive to intensity-dependent changes in the refractive index (as a result of third-order nonlinear polarizability or thermal effects) which lead to self-focusing or defocusing of the beam. Alternatively, if the detector collects all the light from the sample (“open-aperture” setup), then the output only reflects the intensity-dependent transmission, and can be used to measure two-photon absorption cross-sections. In this thesis, we studied the photophysical property and two-photon absorption cross-section for a series of AuI-CuI, AuI-AgI and AgI-CuI heterometallic alkynyl-diphosphine (diphosphine = PPh2-(C6H4)n-PPh2, n = 1, 2, 3) clusters (Chapter 3-7), which display a very intriguing structural pattern based on the heterometallic [AuxMy(C2Ph)2x]y-x fragments “wrapped” by the [Au3(diphosphine)3]3+ “belts”. As results, these complexes exhibit large two-photon absorption cross-sections and intense phosphores due to the transition involving metal-ligand charge transfer such that the heavy metal (Au) enhances spin-orbit coupling. More importantly, owing to fully protected chromophore by the bulky ancillary and bridging ligands, the phosphorescence is nearly inert to oxygen quenching. In combination the intensive phosphorescence intensity, minor O2 quenching property and the two-photon absorption property demonstrate these compounds with promising potential in two-photon emission imaging as well as phosphorescence dyes in time-resolved imaging.口試委員會審定書 I謝 II要 IIIBSTRACT IVIGURE CAPTIONS ACHEME CAPTIONS IABLE CAPTIONS JHAPTER 1. EXPERIMENTAL SETUP OF OPEN-APERTURE Z-SCAN TECHNIQUE 1.1 Introduction 1.2 Experimental Setup and Automation of Open-Aperture Z-scan Technique 3.2.1 Experimental Setup of Open-Aperture Z-scan Technique 3.2.2 Automation of Open-Aperture Z-scan Technique by LabVIEW 4.3 Analysis of Z-scan for a Thin Nonlinear Medium 9.4 Experimental Results and Discussion 14.5 Conclusion 16.6 References 17HAPTER 2. PRINCIPLES OF OPERATION AND INSTRUMENTATION 18.1 Introduction 18.2 Steady-State Spectroscopy 18.2.1 Absorption of UV-visible Light and the Beer-Lambert Law 18.2.2 Emission Spectra 24.2.3 Excitation Spectra 31.3 Measurement of emission quantum yields 32.4 Time-correlated single photon counting 36.5 Two-photon induced emission (TPIE) method. 43.6 References 47HAPTER 3. INTENSELY LUMINESCENT ALKYNYL- PHOSPHINE GOLD(I)-COPPER(I) COMPLEXES: SYNTHESIS, CHARACTERIZATION, PHOTOPHYSICAL AND COMPUTATIONAL STUDIES 49.1 Abstract 49.2 Introduction 50.3 Experimental Section 52.3.1 General comments 52.3.2 General procedure for the preparation of heterometallic Au-Cu complexes. 53.3.3 Photophysical measurements 53.3.4 Computational details 54.4 Results and Discussion 55.4.1 Synthesis and characterization 55.4.2 Photophysical properties 63.4.3 Computational results 68.5 Conclusion 74.6 References 75HAPTER 4. STUDIES OF TWO-PHOTON PROPERTY OF INTENSELY LUMINESCENT ALKYNYL- PHOSPHINE GOLD(I)-COPPER(I) COMPLEXES 79.1 Abstract 79.2 Introduction 80.3 Experimental Section 83.3.1 Materials 83.3.2 Steady-state measurements. 84.3.3 Two-photon induced emission (TPIE) method. 84.3.4 Open-aperture Z-scan method. 86.4 Results and discussion 89.4.1 Steady-State Spectra 89.4.2 TPIE measurements 92.4.3 Z-scan measurements 96.4.4 Discussions 97.5 Conclusion 101.6 References 102HAPTER 5. INTENSELY, OXYGEN INDEPENDENT PHOSPHORESCENT GOLD(I)-SILVER(I) COMPLEX: “TRAPPING” AN AU8AG10 OLIGOMER BY TWO GOLD-ALKYNYL-DIPHOSPHINE MOLECULES 108.1 Abstract 108.2 Introduction 109.3 Experimental Section 109.3.1 General comments 109.3.2 General procedure for the preparation of heterometallic Au-Ag complexes 110.3.3 Photophysical measurements 112.3.4 Computational details 113.4 Results and discussion 114.4.1 Synthesis and characterization 114.4.2 Photophysical properties 120.4.3 Computational results 124.4.4 Two-photon absorption properties 127.5 Conclusion 129.6 References 130HAPTER 6. A LUMINESCENT AU(I)–AG(I) ALKYNYL- DIPHOSPHINE AGGREGATE: A REDUCTIVE FUSION OF TWO HETEROMETALLIC CLUSTERS 134.1 Abstract 134.2 Introduction 134.3 Experimental Section 135.3.1 Photophysical measurements 135.3.2 Computational details 136.4 Results and discussion 137.4.1 Synthesis and characterization 137.4.2 Photophysical properties 140.4.3 Computational results 142.4.4 Two-photon absorption properties 144.5 Conclusion 146.6 References 147HAPTER 7. SYNTHESIS, PHOTOPHYSICAL AND THEORETICAL STUDIES OF LUMINESCENT SILVER(I)−COPPER(I) ALKYNYL-DIPHOSPHINE COMPLEXES 151.1 Abstract 151.2 Introduction 152.3 Experimental Section 154.3.1 General comments 154.3.2 General procedure for the preparation of heterometallic Ag-Cu complexes 154.3.3 Photophysical measurements 157.3.4 Computational details 158.4 Results and discussion 158.4.1 Synthesis and characterization 158.4.2 Photophysical properties 167.4.3 Computational results 173.5 Conclusion 178.6 References 1794468121 bytesapplication/pdfen-USZ-scan量測技術雙光子吸收異種金屬錯合物金(I)-銅(I)錯合物金(I)-銀(I)錯合物銀(I)-銅(I)錯合物Z-scan techniquetwo-photon absorptionheterometallic complexesAu(I)-Cu(I) complexesAu(I)-Ag(I) complexesAg(I)-Cu(I) complexesthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/187506/1/ntu-98-R96223123-1.pdf