旋環雙芴基衍生物之合成與性質探討

Syntheses and Property Studies of Spirobifluorene Derivatives

彭楹芝(Ying-Chu Peng)

指導教授 ： 汪根欉

國立臺灣大學/理學院/化學研究所/碩士(2004年)

https://doi.org/10.6342/NTU.2004.00916

摘要

本研究是以旋環雙芴作為分子的主體架構，並利用原有的十字交叉構形，搭配適當的原子或芳香基團進行修飾，而衍生三個部分。
第一部分是引入吡啶作為配位基的化合物L可和銀離子形成一維的polymeric metal-organic framework，組成基本單元為8 × 8 Å的正方形扭曲孔洞。
第二部分則是以引入氮原子於旋環雙芴架構的化合物14作為銥金屬錯合物的配位基，希望能藉由其立體障礙，增加分子在固態時的放光效率。
第三部分則是以三聚旋環雙芴化合物做為主體，於其共軛主鏈引入高電子親和力氮原子，並探討此做法對於化合物T1a-N光物理，電化學，以及熱性質的影響。在光物理性質方面變化不大；而在電化學性質方面，氮原子之高陰電性使得分子LUMO能階降低，對電子的接受能力增加，而有較佳的親電子性。

關鍵字

旋環雙芴基衍生物

並列摘要

There are three parts in this thesis. First of all, the synthesis and structural characterization of a novel right angle ligand, 2,2’-bis(4-pyridinyl)-9,9’-spirobifluorene (L) are reported. Treatment of the racemic ligands with Ag(I) ions leads to the formation of an 1D polymeric metal-organic framework with square architecture. The structure of the square analyzed by single crystal X-ray analysis has revealed that the dimensions of the distorted square cavity are ca. 8 ´ 8 Å.
Secondary, the compound 1-aza-9,9-spirobifluorene 14 is synthesized, which may present as the potential ligand of iridium(Ш) complexes for electrophospherescent materials.
Finally, the compound T1a-N based on ter(9,9-ditolylfluorene) as the core with highly electronegative nitrogen atom is synthesized. The nitrogen atom of the compound T1a-N has little influence on the photophysical property when compare to that of ter(9,9-ditolylfluorene), if T1a-N study on cyclic voltammetry has indicated the LUMO energy level is lower than that of ter(9,9-ditolylfluorene), which may be benefical for electron injection.

並列關鍵字

Spirobifluorene

參考文獻

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