π鍵結橋樑效應對蒽-五苯荑衍生物之晶體結構及光致機械力螢光變色之探討

Study on the Crystal Structure and Photomechanofluorochromism of Anthracene Pentiptycene Derivatives: Effects of the π-linkers

鄭巧旻(Chiao-Min Cheng)

指導教授 ： 楊吉水

國立臺灣大學/理學院/化學研究所/碩士(2020年)

https://doi.org/10.6342/NTU202003528

摘要

近年來，刺激響應材料受到科學家的關注，因為其具有多樣化的應用潛力如感應器、光學記憶材料及加密/解密材料等等。常見的外力如光、熱、機械力或是化學蒸氣等等。本實驗室先前所發表的文獻中，以五苯荑連接蒽的化合物1-AnPC8分子，經過光照反應形成二聚體時，有如機械力施加而改變分子的排列，影響了其螢光放光，稱為光致機械力螢光變色 (photomechanofluorochromism, PMFC)，這樣特殊的光致機械力螢光變色性質為光控智能材料開啟新的篇章。
本論文試圖探討分子結構上的變化對於晶體結構的影響，以及其對光致機械力螢光變色行為的容忍程度。而分子結構的變化則藉由改變五苯荑與蒽之間的π鍵結橋樑為策略。我們成功合成了兩個目標化合物: YYP及EP。結果顯示，以參鍵延伸共軛的化合物YYP，在固態下放光顏色分布於藍色到綠色之間，顯示了延伸共軛影響到蒽與蒽之間的排列，較不利於進行 [4+4] 光二聚體反應，而減弱了光致機械力螢光變色性質。相反地，將1-AnPC8的參鍵改為雙鍵的分子EP則具有明顯的光致機械力螢光變色的性質。然而，我們發現延伸參鍵後，使得晶體有不同的堆疊外也有不同的溶劑 (客體) 參與其中，具有五種同質多形體。在YYP晶體中發現主要分為兩種堆疊模式，我們試圖分析晶體結構中的排列模式，並且嘗試置換具有電子予體性質的苯胺客體分子，利用主客作用力來調控晶體的放光顏色。

關鍵字

蒽-五苯荑延伸物 ； 光致機械力螢光變色 ； 晶體結構

並列摘要

Stimuli-responsive materials have drawn much attention recently because of their potential applications as biosensors, optical memory materials, and encryption/decryption system. The common stimuli are light, heat, mechanical force and chemical vapor. Our previous work on 1-AnPC8 showed that the fluorescence of the crystal changed as a result of the mechanical stress generated by the [4+4] photodimerization reaction, which is called photomechanofluorochromism, abbreviated as PFMC.
In this work, we tried to investigate crystal packing and photomechanofluorochromisim property of the analogues of 1-AnPC8. We successfully synthesized two new derivatives YYP and EP, which are designed by changing the π-linker between the anthracene and the pentiptycene unit. Our results show that the π-linker can affect the interactions between two adjacent anthracene moieties and the topochemical reaction. On the other hand, YYP shows five polymorphs with different solvent inclusion. We also tried to place electron-donating aniline as the guest molecule to tune the luminescence of the crystal.

並列關鍵字

anthracene-pentiptycene derivatives ； photomechanofluorochromisim ； crystal strucutre

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