含五苯荑炔之寡聚物及鉑錯合物之研究

Abstract

本論文研究含五苯荑取代之共軛寡聚物及鉑錯合物之結構-性質關係。第一章將簡介五苯荑與五苯荑炔之合成及其應用。第二章利用含五苯荑寡苯乙炔在低溫溶劑中的構形變化，研究苯荑取代基之電子性質；第三章則比較含五苯荑寡苯乙炔及含五苯荑寡苯乙二炔之構形變化，以及含五苯荑寡苯乙二炔在玻璃轉化溫度前後構形分布的改變，更進一步地了解苯荑取代基之性質。第四章中，將五苯荑分子引入鉑苯乙炔錯合物中，研究其苯荑分子對於電化學、氧氣感應及固體放光之影響。第五章報導含五苯荑苯雙吡啶鉑錯合物之合成及鑑定，並探討五苯荑取代之位置如何影響聚集體及粉末的放光行為。

The structure-property relationship of pentiptycene-incorporated pi-conjugated oligomers and platinum complexes were reported in this thesis. I will briefly introduce the synthesis and applications of pentiptycene derivative in literatures in Chapter 1. In Chapter 2, intrinsic electronic effect of iptycenyl group will be discussed by elucidating conformational preferences of varied-temperature absorption and emission spectra for oligo(p-phenylene ethynylene)s (OPEs). In Chapter 3, the iptycenyl substituent effect has been extensively studied by comparing the photophysical properties in OPEs and oligo(p-phenylene butadiynylene)s (OPBs). The conformational variation is sensitive to environmental change, that is, the conformation tends to be twisted in fluid liquid and be coplanar in amorphous solids. In Chapter 4, linear platinum acetylides incorporating pentiptycene are reported, and the iptycenyl substituent effect on electrochemistry, oxygen sensing, and solid-state behavior are discussed. The complexes with pentiptycene might be function as ratiometric oxygen sensors. In Chapter 5, cyclometalated platinum complexes incorporating pentiptycenes are reported, and intermolecular interaction in aggregates and solid states in the presence of pentiptycene groups are discussed. In this thesis, we get insight of the intrinsic electronic effect of pentiptycenes which have lower polarizability and localized electron distribution. The shielding effect of iptycenyl substituents is evidenced by reducing oxygen quenching and heterogeneous electron transfer. We are able to design mechanophores by introducing pentiptycene groups.