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標題: | 含五苯荑之全同配位炔基金(I)團簇及錯合物之晶體結構及刺激響應發光性質研究 Crystal Structures and Stimuli-Responsive Luminescence Properties of Pentiptycene-Containing Homoleptic Alkynyl Gold(I) Clusters and Complexes |
作者: | Yu-Hsuan Kang 康伃璇 |
指導教授: | 楊吉水(Jye-Shane Yang) 楊吉水(Jye-Shane Yang | jsyang@ntu.edu.tw | ), |
關鍵字: | 全同配位金(I)團簇,親金作用力,炔基金(I)錯合物,晶體結構,放光性質,刺激響應,力致放光變色, Homoleptic Alkynyl Gold(I) Clusters,Aurophilic interactions,Gold(I) Acetylide complex,Crystal Structures,Luminescence,Stimuli-Responsive Properties,Mechanochromic Luminescence, |
出版年 : | 2022 |
學位: | 碩士 |
摘要: | 本實驗室一直致力於五苯荑衍生物作為刺激響應材料之研究,因五苯荑H形骨架能產生多種堆疊模式且能產生主客體化合物作用力。 金(I)錯合物作為刺激響應材料展現出兩種或多種固態不同放光可逆切換特性,乃因親金作用力很容易受到外部刺激,如蒸氣、外力、熱、光等的影響。親金作用力之定義為金(I)-金(I)距離小於 3.8 Å,大小約為 7~15 kcal/mol,可被應用於超分子自組裝行為。我們最近發表含五苯荑金(I)乙炔基錯合物 (Ph, Ph-C≡C-Au-C≡N-Phip-OC8H17) 之孔洞超分子自組裝晶體結構。此超分子框架包含了Au4 單元,能展現出光誘導金(I)-金(I)鍵縮短,導致了多色光致發光變色。此外,此孔洞通道能容納苯胺衍生物而表現出客體誘導放光增強 (inclusion-induced luminescence enhancement, IILE) 性質。 金(I)炔基錯合物合成過程中,中間體全同配位炔基多核金(I)錯合物(AuC2R)n通常難溶於溶劑,使其結構難以被鑑定。迄今為止,只有三篇文獻報導過團簇晶體結構,其中R基團均是有空間需求的龐大基團。因此,本論文中,我們設計含五苯荑骨架之全同配位炔基多核金(I)團簇 (PaAu)n。結果顯示它具有多同質多形性單晶結構,第一顆晶體包含四核 (PaAu)4和六核金(I)團簇(PaAu)6,第二顆晶體僅由(PaAu)6 組成,且其Au6單元產生了直徑6.1~6.6 Å 的孔洞。團簇 (PaAu)n具有可逆的多階段薰致放光變色行為,放光顏色從綠色到紅色,可歸因於溶劑誘導的結構轉換和主客體作用力變化。 此外,我們使用團簇 (PaAu)n與苯異腈反應後合成一系列IsoPh、IsoOMe 和IsoNMe2錯合物,並與同分異構物Ph比較,以研究孔洞結構及刺激響應性質是否改變。結果顯示IsoPh不具孔洞晶體結構,也不具溶劑客體誘導放光增強性質,可歸因於C≡C鍵和C≡N鍵的鍵長對晶體堆疊產生了巨大影響。 Our group has been working on the development of pentiptycene-derived stimuli-responsive luminescent materials by taking advantage of the H-shaped pentiptycene scaffold in crystal polymorphism and forming host-guest complexes. Gold(I) complexes-based stimuli-responsive materials generally show reversible switching between two or more luminescent states, because the aurophilicity is sensitive to external stimuli, such as vapor, force, heat, and light. Aurophilic bonding is defined to have Au(I)-Au(I) distance between 2.5 and 3.8 Å, corresponding to 7−12 kcal/mol binding energy, which plays an important role in supramolecular self-assembly. We recently reported a gold(I) alkynyl complex (Ph, Ph−C≡C−Au−C≡N−Phip−OC8H17) that forms a porous supramolecular structure in crystals. The framework contains Au4 units, which exhibit photoinduced Au(I)−Au(I) bond contraction, resulting in multicolored luminescence photochromism. The porous channels can also accommodate aniline derivatives, leading to guest inclusion-induced luminescence enhancement. In the process of synthesizing gold(I) alkynyl complexes, the homoleptic alkynyl polynuclear gold (I) intermediate complexes (AuC2R)n are usually insoluble and thus have poor structural characterization. To date, there are only three reports of the crystal structures, in which the R group is bulky and steric demanding. Therefore, in this work, we have designed a pentiptycene-containing homoleptic alkynyl polynuclear gold (I) clusters (PaAu)n. The results show that it is polymorphic with one crystal containing both the tetranuclear (PaAu)4 and the hexanuclear (PaAu)6 units and the other crystal of only (PaAu)6. The Au6 unit in (PaAu)6 creates pores in a diameter of 6.1~ 6.6 Å. The cluster (PaAu)n displays an interesting and reversible multistage vapochromic luminescence from green to red, attributable to solvent-induced cluster transformation and changes in host-guest interactions. Furthermore, (PaAu)n was reacted with phenyl isocyanide to form a series of complexes IsoPh, IsoOMe and IsoNMe2 for comparison with complex Ph, regarding whether the crystal porosity and stimuli-response properties are affected. The results show that both the porosity and the property of inclusion-induced luminescence enhancement are lost, which can be attributed to the impacts of the different C≡C and C≡N bond length. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/85007 |
DOI: | 10.6342/NTU202203922 |
全文授權: | 同意授權(限校園內公開) |
電子全文公開日期: | 2027-09-26 |
顯示於系所單位: | 化學系 |
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