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Changes in the photophysical properties of pyrene ( Py )-octafluoronaphthalene ( OFN ) co-crystals ( Py•OFN ) upon mechanical stimuli are described herein. The Py•OFN co-crystal showed a mechano-induced bathochromic shift in emission, and a similar tendency was observed for the 1,3,6,8-tetramethylpyrene- OFN co-crystal. These shifts are due to disruption of the microscopic molecular orientation in the co-crystal, which allows for excimer formation. In sharp contrast to the parent Py•OFN and methyl-substituted Py-OFN co-crystals, no mec