Multistimuli Two-Color Luminescence Switching via Different Slip-Stacking of Highly Fluorescent Molecular Sheets

• Published in: Journal of the American Chemical Society Vol. 132; no. 39; pp. 13675 - 13683
• Main Authors: Yoon, Seong-Jun, Chung, Jong Won, Gierschner, Johannes, Kim, Kil Suk, Choi, Moon-Gun, Kim, Dongho, Park, Soo Young
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 06.10.2010; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Multidisciplinary; Color; Fluorescent Dyes - chemical synthesis; Fluorescent Dyes - chemistry; Hydrogen Bonding; Luminescence; Molecular Structure; Particle Size; Physical Sciences; Quantum Theory; Science & Technology; Stilbenes - chemical synthesis; Stilbenes - chemistry; Surface Properties; COLORS; REVERSIBLE MECHANOCHROMIC LUMINESCENCE; FILMS; PHOSPHORESCENT; CYANO-SUBSTITUTED DIPHENYLBUTADIENES; OPTICAL-PROPERTIES; PACKING; PHOTOLUMINESCENT; EMISSION; ORGANIC-CRYSTALS
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/ja1044665

Color tuning and switching of the solid-state luminescence of organic materials are attractive subjects for both the fundamental research and practical applications such as optical recording. We report herein cyanostilbene-based highly luminescent molecular sheets which exhibit two-color fluorescence switching in response to pressure, temperature, and solvent vapor. The origin for the multistimuli luminescence switching is the two-directional shear-sliding capability of molecular sheets, which are formed via intermolecular multiple C−H···N and C−H···O hydrogen bonds. The resulting two distinctive crystal phases are promoted by different modes of local dipole coupling, which cause a substantial alternation of π−π overlap. These changes can be directly correlated with the subsequent intermolecular excitonic and excimeric coupling in both phases, as demonstrated by an in-depth theory-assisted spectroscopic and structural study. Finally, we have prepared a first device demonstrator for rewritable fluorescent optical recording media which showed multistimuli luminescence tuning with fast response. Our multistimuli responsive system is unique in terms of the slip-stacking of molecular sheets and thus provides a novel concept of rewritable fluorescent optical recording media.