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Upon grinding, the non-radiative deactivation pathways were obviously blocked, with a non-radiative rate constant of knr =2.9× 10ˆ8 sˆ1 (Fig. S6,† τ= 3.0 ns, ΦPL = 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–ethanol was used as the pressure transmittingmedium. As depicted in Fig. 4b, the Raman absorption band at 1652 cmˆ1 was assigned to the C=O 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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团子小姐: 金币+10, 翻译EPI+1, ★★★★★最佳答案, 谢谢 2014-10-15 20:09:56
团子小姐: 金币+10, 翻译EPI+1, ★★★★★最佳答案, 谢谢 2014-10-15 20:09:56
| 在研磨时,明显阻断了非放射失活的途径,非放射速率常数KNR= 2.9×10^8 s^1(图S6,†τ= 3.0纳秒,ΦPL=12.3%),明显比原始晶体小。因此,有人提出,TPA-CO晶体的分子构象在研磨时变成为平面。这一建议在扩散反射吸收光谱中得到进一步证实,表现为约9nm的轻微红移(图4a)。用Raman光谱进一步研究了TPA-CO晶体在流体静压力作用下的分子构象变化。对具有0.5毫米钻石底尖的金刚石压腔(DAC)进行高压实验。用一红宝石芯片将一小片晶体加载到DAC,以确定现场压力校准。用甲醇 - 乙醇混合物(4:1)作为压力传递发介质。如图4b所示,在正常压力下,在1652 CM^1的Raman吸收带被定为C = O的伸缩模式。有趣的是,随着压力增加至1.51 GPa,这条带转移到较低频率的1649 CM^1,而其它带则被转移到更高的频率。对应于电子离域的扩展而发生的这些变化,又导致了二苯甲酮的构象平面化。 |
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