Multi-Responsive Luminescent Material (多重感應之固態發光材料)
Pentiptycene has a non-planar rigid backbone which might induce different packing modes in the solid state, and thus is an excellent scaffold for the design of mechanochromic luminescent materials. Also, because of the cavities created by U- and V-shape notches, which are suitable for host-guest interaction, pentiptycene has potential for sensing application. Our recently published papers below give a preliminary but typical illustration.
In the first example, we combine pentiptycene and anthracene to construct the molecule in figure (a). In the solid state, it can form exciplex with different anilines, providing a fluorescence change from green to red. Mechanical grinding also decreases its reactivity to guest molecules and thus a memory effect can be achieved. Like the fruit painting below, we unprecedentedly present five colors (red, orange, yellow, green and black) at the same time.
The second example is shown in figure (b). The pristine and ground powders of the molecule have yellow and blue fluorescence, respectively. Controlling the extent of grinding, we can obtain near-pure white emission. It also has two polymorphs, the yellow and green emissive single crystals. Under UV irradiation, the products formed by the photochemical reaction cause stress in the bulk crystal, which turns the fluorescence into blue and red respectively. This special phenomenon is termed as photomechanochromism. The fluorochromicity is demonstrated by the angelfish patterning.
We also utilize pentiptycene in metallorganic system to form the platinum complex in figure (c). After the molecule is ground or fumed by benzene vapor, its packing can be altered and the phosphorescence interconverts among red, orange and yellow. Such benzene-responsive Pt complexes are rarely reported in literature.
Our lab is dedicated to developing pentiptycene derivatives. We hope to achieve more colorful luminescence change and more diversified regulation to expand the application of these smart materials.
In the first example, we combine pentiptycene and anthracene to construct the molecule in figure (a). In the solid state, it can form exciplex with different anilines, providing a fluorescence change from green to red. Mechanical grinding also decreases its reactivity to guest molecules and thus a memory effect can be achieved. Like the fruit painting below, we unprecedentedly present five colors (red, orange, yellow, green and black) at the same time.
The second example is shown in figure (b). The pristine and ground powders of the molecule have yellow and blue fluorescence, respectively. Controlling the extent of grinding, we can obtain near-pure white emission. It also has two polymorphs, the yellow and green emissive single crystals. Under UV irradiation, the products formed by the photochemical reaction cause stress in the bulk crystal, which turns the fluorescence into blue and red respectively. This special phenomenon is termed as photomechanochromism. The fluorochromicity is demonstrated by the angelfish patterning.
We also utilize pentiptycene in metallorganic system to form the platinum complex in figure (c). After the molecule is ground or fumed by benzene vapor, its packing can be altered and the phosphorescence interconverts among red, orange and yellow. Such benzene-responsive Pt complexes are rarely reported in literature.
Our lab is dedicated to developing pentiptycene derivatives. We hope to achieve more colorful luminescence change and more diversified regulation to expand the application of these smart materials.
五苯荑 (pentiptycene) 具有剛硬的非平面骨架，使分子在堆積時具有不同的可能性，能作為力致放光變色 (mechanochromic luminescence) 的研究對象。同時，U和V形凹槽所製造的孔洞，使得外界客體 (guest) 容易進入其中，可能造成蒸氣放光變色 (vapochromic luminescence)，極有潛力應用於感測材料。最近本實驗室發表的三篇論文，為初步但極具代表性的實例。
例如圖 (a) 的分子，將五苯荑與蒽結合，在固態下能與不同的苯胺蒸氣作用，使螢光產生綠色到紅色的變化。且經由輾磨能降低分子與客體的作用性，達到記憶螢光顏色的效果，如下方的水果圖畫，將五種顏色 (紅、橙、黃、綠、黑) 同時呈現，是前所未有的創舉。
圖 (b) 中的分子在輾磨前後螢光顏色分別是黃色及藍色，控制輾磨的程度我們可以得到近乎白色的放光。此分子還具有多形態 (polymorph)，有黃色及綠色螢光的單晶，當紫外光照射發生光反應時，產物對整體晶格造成擠壓，分別產生藍色及紅色螢光，是相當特別的 photomechanochromism。其豐富的顏色變化可由神仙魚的圖案來展示。
圖 (c) 中的分子，將五苯荑應用於有機金屬系統，形成鉑錯合物。將分子輾磨或是薰上苯蒸氣能改變其堆疊狀況，使得磷光在紅橙黃三者之間互相轉換。在此類鉑錯合物中，對於苯蒸氣有反應性之例子相當罕見。
本實驗室積極開發相關之五苯荑衍生物，期望達成更豐富的光色變化，以及更多元的調控方式，拓展此類智慧材料的應用價值。
例如圖 (a) 的分子，將五苯荑與蒽結合，在固態下能與不同的苯胺蒸氣作用，使螢光產生綠色到紅色的變化。且經由輾磨能降低分子與客體的作用性，達到記憶螢光顏色的效果，如下方的水果圖畫，將五種顏色 (紅、橙、黃、綠、黑) 同時呈現，是前所未有的創舉。
圖 (b) 中的分子在輾磨前後螢光顏色分別是黃色及藍色，控制輾磨的程度我們可以得到近乎白色的放光。此分子還具有多形態 (polymorph)，有黃色及綠色螢光的單晶，當紫外光照射發生光反應時，產物對整體晶格造成擠壓，分別產生藍色及紅色螢光，是相當特別的 photomechanochromism。其豐富的顏色變化可由神仙魚的圖案來展示。
圖 (c) 中的分子，將五苯荑應用於有機金屬系統，形成鉑錯合物。將分子輾磨或是薰上苯蒸氣能改變其堆疊狀況，使得磷光在紅橙黃三者之間互相轉換。在此類鉑錯合物中，對於苯蒸氣有反應性之例子相當罕見。
本實驗室積極開發相關之五苯荑衍生物，期望達成更豐富的光色變化，以及更多元的調控方式，拓展此類智慧材料的應用價值。
Multicolor Fluorescence Writing Based on Host-Guest Interactions and Force-Induced Fluorescence-Color Memory
Matsunaga, Y.; Yang, J.-S.
Angew. Chem. Int. Ed. 2015, 54, 7985-7989.
Photomechanochromic vs Mechanochromic Fluorescence of a Unichromophoric Bimodal Molecular Solid: Multicolor Fluorescence Patterning
Hsu, L.-Y.; Maity, S.; Matsunaga, Y.; Hsu, Y.-F.; Liu, Y.-H.; Peng, S.-M.; Shinmyozu, T.; Yang, J.-S.
Chem. Sci., 2018,9, 8990-9001.
Excimer-Monomer Photoluminescence Mechanochromism and Vapochromism of Pentiptycene-Containing Cyclometalated Platinum(II) Complexes
Lin, C.-J.; Liu, Y.-H.; Peng, S.-M.; Shinmyozu, T.; Yang, J.-S.
Inorg. Chem. 2017, 56, 4978-4989.
An Elastic Organic Crystal Enables Macroscopic Photoinduced Crystal Elongation
C.-H. Wang; Y.-H. Hu; C.-Y. David Lu; J.-S. Yang.
J. Am. Chem. Soc. 2023, 145, 6024-6028
Matsunaga, Y.; Yang, J.-S.
Angew. Chem. Int. Ed. 2015, 54, 7985-7989.
Photomechanochromic vs Mechanochromic Fluorescence of a Unichromophoric Bimodal Molecular Solid: Multicolor Fluorescence Patterning
Hsu, L.-Y.; Maity, S.; Matsunaga, Y.; Hsu, Y.-F.; Liu, Y.-H.; Peng, S.-M.; Shinmyozu, T.; Yang, J.-S.
Chem. Sci., 2018,9, 8990-9001.
Excimer-Monomer Photoluminescence Mechanochromism and Vapochromism of Pentiptycene-Containing Cyclometalated Platinum(II) Complexes
Lin, C.-J.; Liu, Y.-H.; Peng, S.-M.; Shinmyozu, T.; Yang, J.-S.
Inorg. Chem. 2017, 56, 4978-4989.
An Elastic Organic Crystal Enables Macroscopic Photoinduced Crystal Elongation
C.-H. Wang; Y.-H. Hu; C.-Y. David Lu; J.-S. Yang.
J. Am. Chem. Soc. 2023, 145, 6024-6028