Center for Artificial Low Dimensional Electronic Systems, Institute for Basic Science (IBS), Pohang, 37673, Republic of Korea.
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang, 37673, Republic of Korea.
Sci Rep. 2017 May 31;7(1):2582. doi: 10.1038/s41598-017-02718-9.
Synthesis of morphologically well-defined crystals of metalloporphyrin by direct crystallization based on conventional anti-solvent crystallization method without using any additives has been rarely reported. Herein, we demonstrate an unconventional and additive-free synthetic method named reverse anti-solvent crystallization method to achieve well-defined zinc-porphyrin cube crystals by reversing the order of the addition of solvents. The extended first solvation shell effect mechanism is therefore suggested to support the synthetic process by providing a novel kinetic route for reaching the local supersaturation environment depending on the order of addition of solvents, which turned out to be critical to achieve clean cube morphology of the crystal. We believe that our work not only extends fundamental knowledge about the kinetic process in binary solvent systems, but also enables great opportunities for shape-directing crystallization of various organic and organometallic compounds.
形态良好的金属卟啉晶体的合成通常是基于反溶剂结晶法，通过直接结晶得到，而无需使用任何添加剂。然而，很少有报道采用这种常规方法来制备金属卟啉晶体。在此，我们提出了一种反常规且无需添加任何添加剂的合成方法，即反相抗溶剂结晶法，通过反转溶剂添加顺序来实现锌卟啉立方体晶体的良好形态。因此，我们提出了扩展的第一溶剂化壳效应机制来支持合成过程，为达到局部过饱和度环境提供了一种新的动力学途径，这取决于溶剂添加顺序，这对于获得晶体的清洁立方形态至关重要。我们相信，我们的工作不仅扩展了关于二元溶剂体系中动力学过程的基本知识，而且为各种有机和有机金属化合物的形状导向结晶提供了很好的机会。
