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X-ray diffraction and DSC analysis To gain an insight into the PFC behaviour of FLA-Cn solids, powder wide-angle X-ray diffraction (PXD) and differential scanning calorimetry (DSC) experiments were conducted on the ground and pristine solids. The PXD patterns of pristine FLA-C3 and FLA-C5 solids show sharp and intense reflections, indicative of their well-ordered microcrystalline structures (Fig. 6a). In contrast, the ground samples display broad and featureless diffractograms reflecting notable amorphous features. This indicates that grinding has induced the phase transition of FLACn solids between crystalline and amorphous states, which should be responsible for the PFC behaviour of FLA-Cn solids. The formation of amorphous state upon grinding was also confirmed by DSC experiments. As shown in Fig. 6b, no additional thermal transitions could be detected for all pristine solids before the isotropic melt transition (Tm); however, there is clearly one exothermic transition peak at the lower-temperature region for ground FLA-C3 and FLA-C5 solids. This broad exothermic peak (Tc) is ascribed to the cold-crystallization of amorphized FLA-Cn solids upon heating. Amorphized FLA-C3 and FLA-C5 solids have high Tc values, which result in their stable PFC behaviour at room temperature. It is known that the Tc is obviously lower than the Tm of a compound, and the ground FLA-C12 solid could cold-crystallize at or below room temperature since its isotropic melt point is only about 65 C. Thus, the amorphized FLA-C12 solid induced by grinding is in a thermodynamically and dynamically unstable morphology. This is reason why ground FLA-C12 solid exhibits spontaneously recovering fluorescence properties at room temperature. |
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