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For the melted powders,due to the rapid cooling,the molecules may have quickly aggregated to become amorphous,which tends towards a more planar structure.This proposal was further supported by the poor reflection peaks of the PXRD pattern in Fig. 3B. During the long annealing process (Film-h),the molecules in the powder might restructure themselves andadopt a more distorted conformation to fit into the crystalline lattice, which enables the powder to emit a weak fluorescence.Uniquely, the quantum yields of samples Melted-m and the drop-casting film were evidently higher than that of the ground powder, which could be attributed to the uneven grinding force applied to the pristine powder and the spontaneous recovery ability of the ground powder. As depicted in Fig. S7,† the emission intensity of the freshly ground powder was spontaneously reduced with a slight blue-shift as time passed. Thus,the obtained quantum yields become smaller. In a word, the solid-state TPA-CO with larger twist angles exhibited a tunable molecular conformation, which led to a change in intramolecular conjugation and intermolecular interactions under external stimuli. |
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团子小姐: 金币+9, 翻译EPI+1, ★★★★★最佳答案, 谢谢 2014-10-16 12:09:34
团子小姐: 金币+9, 翻译EPI+1, ★★★★★最佳答案, 谢谢 2014-10-16 12:09:34
| 对于熔融的粉末，由于快速冷却时分子可能很快聚集成为无定形的状态，这往往趋于形成一平面结构。这一设想得到了图3B的支持：在PXRD图谱中，反射峰很差。在漫长的退火工艺（Film-h）中，粉末中的分子可能转型，并采用更扭曲构象装配到结晶晶格，从而使该粉末发出微弱的荧光。很独特的是，样品的量子产率Melted-m和滴流延制膜均明显高于研磨的粉末，这可能是由于施加到原始粉末的研磨力不均匀以及研磨粉末的自发恢复能力。如图S7†所示，新鲜磨碎粉末的发光强度随着时间的流逝被自发地减弱，并出现轻微的蓝移。因此，所获得的量子产率变小。总之，具有较大扭转角的固态TPA-CO具有一种可调的分子构象，在外部刺激作用下可以导致分子内部交联以及分子之间的相互作用。 |
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