Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 138, Issue 19, Pages 6252-6260Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.6b02409
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Funding
- MEXT (Japan) program Strategic Molecular and Materials Chemistry through Innovative Coupling Reactions of Hokkaido University
- Program for Fostering Researchers for the Next Generation
- JSPS KAKENHI [15H03804, 15K13633, 26810042]
- Grants-in-Aid for Scientific Research [26810042] Funding Source: KAKEN
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Mechanoinduced phase transitions of emissive organic crystalline materials have received much attention. Although a variety of such luminescent mechanochromic compounds have been reported, it is challenging to develop mechanochromic compounds with crystal-to-crystal phase transitions in which precise structural information about molecular arrangements can be obtained. Here, we report a screening approach to explore mechanochromic compounds exhibiting a crystal-to-crystal phase transition. We prepared 48 para-substituted (R-1) phenyl[para-substituted (R-2) phenyl isocyanide]gold(I) complexes designated R-1-R-2 (six R-1 and eight R-2 substituents) and then performed three-step screening experiments. The first screening step was selection of emissive complexes under UV light, which gave 37 emissive R-1-R-2 complexes. The second screening step involved evaluation of the mechanochromic properties by emission spectroscopy. Twenty-eight complexes were found to be mechanochromic.. The third screening step involved. preparation of single crystals, reprecipitated powders, and ground powders of the 28 mechanochromic R-1-R-2 complexes. The changes in the powder diffraction patterns of these complexes induced by mechanical stimulation were investigated. Two compounds exhibited a crystal-to-crystal phase transition upon mechanical stimulation, including the previously reported H-H complex. Single crystals of the as-prepared and ground forms of the newly discovered CF3-CN complex were obtained. Density functional theory calculations indicated that the mechanoinduced red-shifted emission of CF3-CN is caused by formation of aurophilic interactions. Comparison of the crystal structures of CF3-CN with those of the other complexes suggests that the weaker intermolecular interactions in the as-prepared form are an important structural factor for the observed mechanoinduced crystal-to-crystal phase transition.
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