Fluorenone Organic Crystals: Two-Color Luminescence Switching and Reversible Phase Transformations between 蟺鈥撓€ Stacking-Directed Packing and Hydrogen Bond-Directed Packing

详细信息    查看全文

• 作者：Mao-Sen Yuan ; Dong-En Wang ; Pengchong Xue ; Wenji Wang ; Jian-Chun Wang ; Qin Tu ; Zhiqiang Liu ; Yang Liu ; Yanrong Zhang ; Jinyi Wang
• 刊名：Chemistry of Materials
• 出版年：2014
• 出版时间：April 8, 2014
• 年：2014
• 卷：26
• 期：7
• 页码：2467-2477
• 全文大小：771K
• 年卷期：v.26,no.7(April 8, 2014)
• ISSN：1520-5002

文摘

Organic solid-state luminescence switching (SLS) materials with the ability to reversibly switch the luminescence by altering the mode of molecular packing without changing the chemical structures of their component molecules have attracted considerable interest in recent years. In this work, we design and synthesize a new class of 2,7-diphenylfluorenone derivatives (compounds 1鈥?b>6) that exhibit prominent aggregation-induced emission (AIE) properties with high solid-state fluorescence quantum yields (29鈥?5%). Among them, 2,7-bis(4-methoxyphenyl)-9H-fluoren-9-one (2) and 2,7-bis(4-ethylphenyl)-9H-fluoren-9-one (6) display reversible stimuli-responsive solid-state luminescence switching. Compound 2 transforms between red and yellow crystals (the emission wavelength switches between 601 and 551 nm) under the stimuli of temperature, pressure, or solvent vapor. Similarly, compound 6 exhibits SLS behavior, with luminescence switching between orange (571 nm) and yellow (557 nm). Eight X-ray single-crystal structures, characterization of the photophysical properties, powder X-ray diffraction, and differential scanning calorimetry provide insight into the structure鈥損roperty relationships of the solid-state fluorescence behavior. The results indicate that the variable solid-state luminescence of the fluorenone derivatives is attributed to the formation of different excimers in different solid phases. Additionally, the stimuli-responsive reversible phase transformations of compounds 2 and 6 involve a structural transition between 蟺鈥撓€ stacking-directed packing and hydrogen bond-directed packing. The results also demonstrate the feasibility of our design strategy for new solid-state luminescence switching materials: introduction of both 蟺鈥撓€ stacking and hydrogen bonding into an AIE structure to obtain a metastable solid/crystalline state luminescence system.