Mechanofluorochromism of 1-Alkanoylaminopyrenes

• Published in: Chemphyschem Vol. 16; no. 14; pp. 3038 - 3043
• Main Authors: Nagata, Eisuke, Takeuchi, Shugo, Nakanishi, Takayuki, Hasegawa, Yasuchika, Mawatari, Yasuteru, Nakano, Hideyuki
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 05.10.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: alkanoylaminopyrene; Crystal structure; Diffraction; excimers; fluorescence; hydrogen bonds; mechanofluorochromism; mechanofluorochromism; fluorescence; alkanoylaminopyrene; hydrogen bonds; excimers
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201500383

To create a new series of mechanofluorochromic materials and to elucidate the mechanism of the phenomenon of mechanofluorochromism, 1‐alkanoylaminopyrenes including 1‐acetylaminopyrene (AAPy), 1‐octanoylaminopyrene (OAPy), and 1‐stearoylaminopyren (SAPy) were prepared. It was found that these materials exhibited mechanofluorochromism with emission colors in the crystalline samples changing reversibly from bluish purple to yellowish green, which could be induced by mechanical grinding. X‐ray crystal structure analysis, electronic absorption, and fluorescence spectroscopies, as well as fluorescence lifetime analysis and powder X‐ray diffraction analysis of AAPy suggested that the present mechanofluorochromism was caused by developing crystal defects through grinding. Intermolecular hydrogen bonds were suggested to play an important role in the occurrence of mechanofluorochromism, suppressing the face‐to‐face overlapping of pyrene moieties to form excimers in the pristine crystal. Exhibitionist: 1‐Alkanoylaminopyrenes (AAPy, OAPy, and SAPy), as simple monosubstituted pyrenes, are found to exhibit mechanofluorochromism. Intermolecular hydrogen bonds through amido groups were suggested to play an important role in the exhibition of mechanofluorochromism.