- 學位論文
1. 新穎磷光鉑二價錯合物含磷配位基-合成、結構及光物理性質探討 2. 新穎深藍磷光鉑四價錯合物
1. Novel Phosphorescent Platinum (II) Complexes Bearing Phosphine Ligands: Synthesis, Structures and Photophysical Properties 2. Novel Deep Blue Phosphorescent Platinum (IV) Complexes
摘要
我們合成出一系列新穎鉑二價帶有磷配位基的磷光金屬錯合物。磷配位基上的取代基會影響它們的固態放光波長，但對於HOMO和LUMO的能階差卻影響不大。P(Ph-F)3是一個具有極佳立體障礙的配位基，可以防止Pt-Pt interaction 和π-π interaction，以免造成放光光譜的紅位移。我們也利用密度泛函理論計算去探反應機構及不同陰離子對錯合物的放光影響。然而，根據DFT理論計算的結果，PtdfppyCNPPh3 具有很高的能階差，在有機發光二極體的領域中相當適合作為藍光磷光材料。我們努力嘗試合成PtdfppyCNPPh3 ，但卻失敗，幸運的是卻從中得到高亮度的聚集金屬錯合物。我們改變反應條件且利用自組裝反應去提高反應產率。所合成出的兩個聚集金屬錯合物具有獨特的平行四邊形結構，且以Pt-CN-Ag為單位，是文獻上第一個例子。另一方面，我們也利用氧化加成反應合成出鉑四價金屬錯合物。當鉑二價金屬錯合物氧化成四價後，MLCT能階會被誘導變大，而造成放光波長也會藍移許多，尤其是PtdfppyacacCH3CN，它的最短放光波長在437 nm，是文獻上眾多含有2,4-diflourophenyl pyridyl 配位基的金屬錯合物中最藍的放射波長。
並列摘要
A series of novel phosphorescent platinum (II) complexes bearing phosphine ligands were synthesized. Photoluminescence of platinum (II) complexes in solid state are influenced by substituents on phosphine ligands, but the energy gap between HOMO and LUMO isn’t. Tri-(4-flourophenyl) phosphine has the best steric effect for preventing Pt-Pt interaction and π-π interaction to make red shift in photoluminescence. DFT-calculation was measured on several of platinum (II) complexes to discuss the reaction mechanism and the effect of different types of anions. According to DFT-calculation, PtdfppyCNPPh3 has the biggest energy gap between HOMO and LUMO, so I tried to synthesize PtdfppyCNPPh3 which can be a deep blue phosphorescent material in OLED. The synthesis of PtdfppyCNPPh3 was unsuccessful, but fortunately, aggregate complex with high luminescence was obtained. We changed reaction condition to promote the yield of aggregate complexes by self-assembly reaction. These two aggregate complexes have unique parellelogramal structure with Pt-CN-Ag unit, which was the first example of Pt-CN-Ag aggregate complex. In other hand, platinum (IV) complexes were synthesized by oxidative-addition process. While platinum (II) complexes were oxidized to platinum (IV) complexes, MLCT gap will be induced to larger. Hence, photoluminescence of platinum (IV) complexes are blue-shifted than that of platinum (II) complexes. Especially, for PtdfppyacacCH3CN, the complex can emit deep blue phosphorescence at 77 K with wavelength of 437 nm, 465 nm, 497nm in which 437 nm was the shortest wavelength of emission with 2,4-diflourophenyl pyridyl ligand.
參考文獻
延伸閱讀
- 林桂民（2009）。磷光鉑二價錯合物含無共軛輔助配位基及氮雜環之合成、結構及光物理性質之探討〔碩士論文，國立清華大學〕。華藝線上圖書館。https://doi.org/10.6843/NTHU.2009.00309
- 甘慧萍（2008）。新型非共軛配位基藍色磷光銥金屬錯合物之合成與其在有機電激發光元件上之應用〔碩士論文，國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-2002201314285601
- 林彥勳（2021）。引入喹喔啉吡唑配位基之二價鉑金屬磷光材料的製備及光物理性質探討〔碩士論文，國立清華大學〕。華藝線上圖書館。https://www.airitilibrary.com/Article/Detail?DocID=U0016-2412202116172544
- 黃崑棋（2007）。二價鋨金屬磷光錯合物的合成與光物理性質的探討〔碩士論文，國立清華大學〕。華藝線上圖書館。https://doi.org/10.6843/NTHU.2007.00472
- 劉信寬（2009）。Novel Synthesis, Crystal Structures and Properies of Organic – Inorganic Hybrid Metal Phosphates and Multi Dimensional Magnesium Coordination Polymers〔碩士論文，中原大學〕。華藝線上圖書館。https://doi.org/10.6840/cycu200900780