楊吉水Yang, Jye-Shane臺灣大學:化學研究所林哲仁Lin, Che-JenChe-JenLin2010-06-302018-07-102010-06-302018-07-102009U0001-2007200914021000http://ntur.lib.ntu.edu.tw//handle/246246/187528本論文之目的為合成一系列 [(C^N)Pt(O^O)] 及其分子模型計算並探討其光化學性質。C^N 為含有對胺基苯乙烯取代之苯吡啶 (PhDM, PhDP, PyDM, PyDP)期為單陰離子之配位基，而O^O為乙醯丙酮配位基。們利用X-ray繞射鑑定化合物PhDP與PtPhDP之晶體結構。DFT與TDDFT理論計算錯合物及其配位基之分子模型與激發態能階，並利用UV-Vis 吸收光譜、放射光譜及反式→順式光致異構化量子產率探討錯合物及其配位基之光化學性質。所有PtII錯合物含有配位基內電荷轉移 (ILCT) 之單重態激發態且錯合物PtPhDM 及PtPhDP相較於錯合物PtPyDM及PtPyDP含有較強的鄰位ILCT性質。有錯合物之磷光光譜是在低溫77 K測得，室溫下之磷光量子產率則非常低 (<10-3)。此外，激發態行為主要是由二苯乙烯或是含氮二苯乙烯部分所主導。激發態去活化路徑是由反式→順式異構化所主導，而跟取代基的位置與種類無關。最低三重激發態為配位基內電荷轉移 (3ILCT) 態。錯合物PtPyDM及PtPyDP之3ILCT激發態之分布主要是區域化在含氮二苯乙烯部分，而錯合物PtPhDM及PtPhDP之3ILCT激發態則是由胺基二苯乙烯至吡啶陽離子非定域分布。以上現象可知，對胺基苯乙烯取代之鉑錯合物其激發態主要是區域化在二苯乙烯及含氮二苯乙烯部分，且可由對位及鄰位共軛效應來解釋其光物理性質。The synthesis, molecular modeling, and photochemical properties of four Pt(II) complexes [(C^N)Pt(O^O)] are reported. C^N is a monoanionic cyclometalating styrene-incorporated phenylpyridine ligand (PyDM, PyDP, PhDM, and PhDP) and O^O is an acetylacetone (acac) ligand. The solid-state structures of PhDP and PtPhDP were characterized by X-ray diffraction. Molecular modeling was carried out with DFT and TD-DFT methods, and photochemical properties were investigated with UV-Vis absorption, steady-state luminescence, and the measurements of trans→cis photoisomerization quantum yield. The lowest singlet excited-state (S1) for all the Pt complexes is of ILCT character and it is more meta-ph ILCT character for PtPhDM and PtPhDP than for PtPyDM and PtPyDP. All PtII complexes show phosphorescence only at 77 K but not at room temperature. The major triplet deactivated pathway is the nonradiative trans→cis isomerization. Furthermore, the excited-state behavior which is independent of the substitution position mainly dictated by the stilbene and azastilbene moiety. The lowest excited state (T1) is an intraligand charge transfer state (3ILCT). The 3ILCT state is localized on the azastilbene moiety for PyDM and PyDP systems but is from aminostilbene to the pyridinium moiety for PhDM and PhDP systems. As a result, the behavior of these systems can be understood by a para vs meta conjugation effect.Table of Contents誌 II文摘要 IIIbstract IVable of Contents Vist of Figures VIIIist of Tables XVist of Schemes XVIIIefinition XIXhapter 1 Introduction 1.1 Photochemistry 1.2 Photochemistry of Stilbene and Stilbene Derivatives 4.3 Photochemistry of Platinum Complexes 19.4 Objective 30hapter 2 Results and Discussion 31.1 Synthesis 31.2 Crystal Structures 36.3 DFT Calculations 41.4 Photochemical Properties of Ligands 50.4.1 Electronic Spectra of Ligands 50.4.2 Quantum Yields and Lifetimes for Ligands 55.5 The Photochemical Properties of Complexes 58.5.1 Electronic Spectra of Complexes 58.5.2 Quantum Yields and Lifetimes for Complexes 73.6 Synthesis of Bridged Stilbene 75hapter 3 Conclusion 79hapter 4 Experimental Section 80.1 Chemicals 80.2 Methods and Instruments 83.2.1 Nuclear Magnetic Resonance, 400 MHz ; Varian 400 or Bruker 400 83.2.2 FT-Infrared Spectrometer ; Varian 640-IR 83.2.3 Elementary Analyzer ; Elementar Vario EL III 84.2.4 High-Resolution MASS 84.2.5 X-Ray Single Crystal Diffractometer 84.2.6 Melting Point Equipment ; Mel Temp II 84.3 Photophysical Methods 85.3.1 UV-Vis Absorption Spectra 85.3.2 Fluorescence Quantum Yield Measurement 85.3.3 Fluorescence Decays 86.3.4 Phosphorescence Spectra 86.3.5 Phosphorescence Decays 86.3.6 Quantum Yield of Photoisomerization 87.3.7 Density Functional Calculation 87.4 Synthesis Procedure 88.4.1 General Procedure 88.4.2 Synthesis and Identification of 4-(N, N–dimethylamino)styrene 90.4.3 Synthesis and Identification of 4-(N, N-diphenylamino)styrene 91.4.4 Synthesis and Identification of 2-(3-bromophenyl)pyridine 93.4.5 Synthesis and Identification of 4-bromo-2-phenylpyridine 94.4.6 Synthesis and Identification of Ligands 96.4.7 Synthesis and Identification of Complexes 99.4.8 Synthesis and Identification of 5-diphenylaminoindene 103hapter 5 References 107ppendix i11345340 bytesapplication/pdfen-US鉑二苯乙烯platinumstilbenethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/187528/1/ntu-98-R96223156-1.pdf