Thermally Robust 3-D Co-DpyDtolP-MOF with Hexagonally Oriented Micropores: Formation of Polyiodine Chains in a MOF Single Crystal

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• 作者：Seung Hyun Chae ; Hyun-Chul Kim ; Young Sun Lee ; Seong Huh ; Sung-Jin Kim ; Youngmee Kim ; Suk Joong Lee
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：January 7, 2015
• 年：2015
• 卷：15
• 期：1
• 页码：268-277
• 全文大小：642K
• ISSN：1528-7505

文摘

A new porphyrin-based Co-MOF, [Co(DpyDtolP)]₆路12H₂O (I), composed of DpyDtolP (5,15-di(4-pyridyl)-10,20-di(4-methylphenyl)porphyrin) was prepared in a high yield and structurally characterized by X-ray crystallography. DpyDtolP is a ditopic N-donor ligand with a large space or gap between the two pyridyl groups at the 5- and 15-positions of the porphyrin backbone. Unlike the pyridyl groups, the 4-tolyl groups in DpyDtolP could not be involved in coordination toward the metal ion. Nevertheless, the presence of these two 4-tolyl groups led to a new infinite three-dimensional framework: Co-MOF (I) with exceptionally high thermal stability at elevated temperature. The single crystals of I maintained their crystallinity even after vacuum drying at 250 掳C. The resulting dried single crystals diffracted X-ray to give the same structural solution as the as-prepared crystals. The robust framework of I contained micropores that were periodically arranged in a hexagonal symmetry. While the evacuated I moderately sorbed N₂ at 77 K, it sorbed 142.8 cm³ g^鈥? (6.37 mmol g^鈥?) of CO₂ at 196 K. The CO₂ sorption isotherms exhibited a very clear step in both the adsorption and desorption branches. A slight hysteretic behavior was observed between the two branches. Furthermore, the crystal structure of CO₂-captured I (I_CO₂) revealed that the linear arrangement of the CO₂ molecules occupied the inside of micropores, thereby indicating the effective CO₂ capture by evacuated I. The evacuated I was also found to be ideal for the encapsulation of iodine molecules in cyclohexane to provide iodine-captured I (I_I₂), which was also characterized by X-ray crystallography. The linear arrangement of polyiodine chains in the micropores was observed, and a single crystal of I_I₂ exhibited electrically conducting behavior. The encapsulation amount of iodine was dependent on the crystal sizes of I. Additionally, the separately prepared microscale sample, micro-I, with a much reduced particle dimension than the bulk I exhibited an enhanced uptake of iodine under the same conditions.