Tailor-made additives (TMAs) have found a role in crystal morphology engineering and control by specific binding to crystal surfaces through stereo-chemical recognition. The utility of TMAs, however, has been largely limited to crystal growth from solutions. In this review, we illustrate examples where TMAs have been used to influence the growth of crystals during cooling of their melts. In solution, the crystal growth driving force is governed by solute supersaturation, which corresponds to the deviation from equilibrium. In growth from melts, however, undercooling is the important thermodynamic parameter responsible for crystallization outcomes, a key difference that can influence the manner in which TMAs affect growth kinetics, crystal morphology, nucleation, enantioselective surface recognition, and the determination of the absolute sense of polar axes. When the crystallization driving force in a melt is small and diffusion is comparatively high, TMAs can exert their influence on well-faceted single crystals with the stereochemical richness observed in solution growth. Under high supercooling, where the driving force is large, ensembles of crystals can grow radially, masking stereochemical information and requiring new optical tools for understanding the influence of TMAs on emerging crystals.

中文翻译：

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用于熔融生长分子晶体的定制添加剂：为什么或为什么不？

定制添加剂 (TMA) 通过立体化学识别与晶体表面特异性结合，在晶体形态工程和控制中发挥着重要作用。然而，TMA 的用途很大程度上仅限于溶液中的晶体生长。在这篇综述中，我们举例说明了 TMA 用于影响熔体冷却过程中晶体生长的例子。在溶液中，晶体生长驱动力由溶质过饱和度控制，这对应于平衡偏离。然而，在熔体生长中，过冷度是决定结晶结果的重要热力学参数，这是一个关键差异，可以影响 TMA 影响生长动力学、晶体形态、成核、对映选择性表面识别以及绝对意义确定的方式。极轴。当熔体中的结晶驱动力较小且扩散较高时，TMAs 可以对具有在溶液生长中观察到的立体化学丰富度的良好刻面单晶发挥影响。在驱动力很大的高过冷度下，晶体集合体可以径向生长，掩盖了立体化学信息，并且需要新的光学工具来了解TMA对新兴晶体的影响。