雙芘取代的多面體聚矽氧烷複合奈米粒子: 探討其晶體的微結構以及光致發光的應用

Abstract

我們利用零價鉑催化的氫化反應使含有矽烷官能基的異丁基多面體聚矽氧烷與含有雙芘取代的雙鍵分子反應而合成出一個單官能基雙芘取代的異丁基多面體聚矽氧烷(蝴蝶狀的BPy-POSS).我們對BPy-POSS的性質做了一連串的研究.從微分掃描卡計 (DSC)中我們可以發現BPy-POSS是一個像高分子一樣,半結晶性的小分子,在放射光譜中也可看出芘類強烈的excimer emission.我們製備出混合不同比例的BPy-POSS和i-Bu POSS的薄膜,並且探討它們的微結構. 經由光學顯微鏡以及原子力顯微鏡,我們觀察出其特殊的蕨葉狀微結構;我們猜想此一蕨葉狀微結構的形成是由於i-Bu POSS和i-Bu POSS 的堆疊.在溶劑揮發到結晶的過程,i-Bu POSS會先結晶作為一個 POSS 的基板,然後BPy-POSS再分散在i-Bu POSS基板的表面上.使用X-ray 散射圖譜以及微分掃描卡計我們也確實可以證明i-Bu POSS和BPy-POSS會微觀相分離的結果.我們利用這種會自組裝的特點形成雙芘的薄膜可應用在硝基芳烴的氣體的偵測.當表面的雙芘暴露在充滿硝基芳烴的蒸氣裡,硝基芳烴很快速了抑制雙芘excimer emission.利用BPy-POSS和i-Bu POSS的自組裝薄膜, 使用少量的BPy-POSS也可以達到不錯的偵測效果.

A bispyrenyl monofunctionalized isobutyl-polyhedral oligomeric silsesquioxane (butterfly-like BPy-POSS) is synthesized by Pt (0)-catalyzed hydrosilylation between silane-monofunctional isobutyl-POSS and bispyrenyl alkene. By DSC, we found that BPy-POSS is a polymer-like semi-crystal molecule. Strong excimer emission was observed in PL spectra. Blends of BPy-POSS and isobutyl-POSS were fabricated to investigate their microstructures. Fern-like microstructures can be seen by OM and AFM; we suspected that the cause of forming fern-like structures is POSS-POSS recognition. During solvent evaporation, i-Bu POSS crystallize as a POSS template, and then BPy-POSS dispersed on the surface of POSS template. The data of XRD and DSC could be an evidence of phase separation of i-Bu POSS and BPy-POSS. We used these self-assembled films to do the application of attachment to nitroaromatic compounds. Upon exposure to nitrobenzene vapor, the films show fast fluorescence quenching. The high performance is based on the microstructure of BPy-POSS and i-Bu POSS on the film surface. Using the self-assembled blend thin films of i-Bu POSS and BPy-POSS, we could achieve the goal of detection of nitrobenzene by using small amount of BPy-POSS.