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Upon grinding, the non-radiative deactivation pathways were obviously blocked, with a non-radiative rate constant of knr =2.9¡Á 10ˆ8 sˆ1 (Fig. S6,† ¦Ó= 3.0 ns, ¦µPL = 12.3%), which was obviously smaller that of the original crystals. Thus, it was suggested that the molecular conformation of the TPA-CO crystals became planar upon grinding. This proposal was further verified by a slight red-shift of approximately 9 nmin the diffuse reflectance absorption spectrum (Fig. 4a). The molecular conformational change of the TPA-CO crystals in responseto hydrostatic pressure was further studied by Raman spectroscopy. The high-pressure experiments were performed in a diamond anvil cell (DAC) with 0.5 mm diamond culets. A small piece of crystal was loaded into the DAC with a ruby chip to determine in situ pressure calibration. A 4 : 1 mixture of methanol¨Cethanol was used as the pressure transmittingmedium. As depicted in Fig. 4b, the Raman absorption band at 1652 cmˆ1 was assigned to the C£½O stretching mode at normal pressure. Interestingly, this band was shifted to the lower frequency of 1649 cmˆ1, whereas other bands were shifted to higher frequencies as the pressure was increased up to 1.51 GPa. The change corresponded to extension of the electron delocalization, which resulted in conformational planarization of benzophenone. |
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