Reverse Anti-solvent Crystallization Process for the Facile Synthesis of Zinc Tetra(4-pyridyl)porphyrin Single Crystalline Cubes

Abstract 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...

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Bibliographic Details
Main Authors: Yohwan Park, Misun Hong, Jin Young Koo, Minkyung Lee, Jinho Lee, Dae Jun Moon, So Hyeong Sohn, Taiha Joo, Woo Taik Lim, Hyunseob Lim, Hee Cheul Choi
Format: article
Language:EN
Published: Nature Portfolio 2017
Subjects:
R
Q
Online Access:https://doaj.org/article/79d4664dbe5e46ad9b5bef7158b6c73d
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Summary:Abstract 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.