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Title: | 含五苯荑之金(I)異腈錯合物晶體結構及光致發光之探討 Studies on the Relationship between Polymorph Crystal Structure and Photoluminescence of Pentiptycene-Containing Gold(I) Isocyanide Complex |
Authors: | Ssu-Ying Chen 陳思穎 |
Advisor: | 楊吉水(Jye-Shane Yang) |
Keyword: | 五苯荑,一價金錯合物,同質多形性, pentiptycene,gold(I) complex,polymorphism, |
Publication Year : | 2019 |
Degree: | 碩士 |
Abstract: | 智能發光材料近年來被廣泛的開發,其放光顏色的變化可受許多不同外部刺激調控如熱致變色 (Thermochromism)、力致變色(mechanochromism) 與薰致變色 (vapochromism)。本實驗室在2015年發表由蒽發光團接上兩個五苯荑基團之分子,其具有力致螢光變色 (mechanofluorochromism) 與薰致螢光變色 (vapofluorochromism) 的性質,主要來自於固態受外力研磨與否改變分子單體或激發雙體主導的放光,或者在苯胺蒸氣下會與苯胺分子形成激發錯體進行放光。相較於有機分子,有機金屬錯合物更具有吸引力,最主要原因是有機金屬錯合物中有許多不同的電子躍遷方式,使得錯合物具有許多不同放光特性。因此,在2017年本實驗室發表出具有力致變色及薰致變色之特性之含有五苯荑基團的鉑(II)錯合物,而此錯合物受外力或苯蒸氣作用造成磷光改變主要是因為π-π作用力的減少,但並沒有金屬-金屬作用力。
本工作設計出具有金屬-金屬作用力之五苯荑錯合物,因此選擇使用金(I)做為中心金屬,主要是因為其結構屬於直線形。我們在金屬端接上苯環,探討是否同時能有π-π作用力的存在,命名為Ph-Au (1)。同時,我們也探討錯合物是否會具有同質多形性、金屬-金屬之間作用力以及測量其力致變色性質。結果顯示Ph-Au (1)具有力致變色的性質且晶體結構可以得知具有金屬-金屬作用力。此外,Ph-Au (1)具有四種晶體結構,且放光性質與金屬和配體共軛性質及電子耦合能力的差異有關。然而,引入較大的五苯荑基團會使得晶體排列上有空間上的限制,造成晶體結構中分子有彎曲的現象產生,這是在金(I)錯合物的例子中是相當少見。 Smart luminescent materials have been widely developed in recent years, and luminescence can be regulated by many different external stimuli such as temperature (thermochromism), pressure (mechanochromism) and organic vapor (vapochromism). A pentiptycene-derived π-conjugated molecule, which is composed of an anthracene group and attached with two pentiptycene moieties, has been previously reported in 2015 to exhibit mechanofluorochromism (MFC) and vapofluorochromism (VFC) properties in its solid state. The MFC behavior of this compound was induced by excimer/monomer transformation, and the VFC behavior resulted from the exciplex formation between aniline vapor. Compared to organic molecules, organometallic complexes are more attractive because of metal ions and organic ligands are expected to exhibit more intriguing luminescence mechanochromism. Therefore, pentiptycene-containing cyclometalated platinum(II) complexes published in 2017 exhibited the mechanochromic and vapochromic luminescence properties. However, the phosphorous luminescence change caused by the external force or benzene vapor is mainly due to the decrease of π-π interaction. In this work, we designed a pentiptycene-containing gold(I) complex 1 and investigated to metal-metal interaction, polymorphism and mechanochromism. The results show that complex 1 exhibits fluorescence turn-on upon grinding and has four different X-ray crystal structure. On the basic of theoretical calculations, we found that the difference of their luminescence was caused by the level of π-orbital interaction and Au-Au interaction. In addition, the bending structure in one of the polymorph is due to the bulky pentiptycene moiety and rarely observed in the reported gold(I) isocyanide systems. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/77201 |
DOI: | 10.6342/NTU201903307 |
Fulltext Rights: | 未授權 |
Appears in Collections: | 化學系 |
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ntu-108-R06223130-1.pdf Restricted Access | 24.6 MB | Adobe PDF |
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