New Multicomponent Porous Architecture of Self-Assembled Porphyrins/Calixarenes Driven by Nickel Ions

详细信息    查看全文

• 作者：Giovanna Brancatelli ; Rita De Zorzi ; Neal Hickey ; Patrizia Siega ; Guglielmo Zingone ; Silvano Geremia
• 刊名：Crystal Growth & Design
• 出版年：2012
• 出版时间：October 3, 2012
• 年：2012
• 卷：12
• 期：10
• 页码：5111-5117
• 全文大小：491K
• 年卷期：v.12,no.10(October 3, 2012)
• ISSN：1528-7505

文摘

A new multicomponent material with nanoporous structure has been synthesized by co-crystallization of a mixture of cationic meso-tetrakis(4-N-methylpyridyl)porphyrin (H₂T₄) and meso-tri(4-N-methylpyridyl)porphyrin (H₂T₃py) with polyanionic 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis(hydroxylcarbonylmethoxy)calix[4]arene (C₄TsTc) in the presence of Ni²⁺ ions. The structural analysis indicates that the overall architecture is assembled by interpenetrated two-dimensional (2D) meshes where the nodes are built up by a central tetracationic H₂T₄ porphyrin with arms hosted in sulphonated rims of four cavitands. The approximately 2D square network is formed by Ni²⁺ ions bridging the calixarene carboxylate rims in a tail-to-tail fashion. The central H₂T₄ stacks with two external H₂T₃py molecules having the neutral pyridine arm N-coordinated to Ni²⁺ ions. These metal centers interconnect the orthogonal 2D meshes by further coordination of calixarene鈥揷arboxylate groups. Self-organization of the new multicomponent material, featuring large channels (60% of volume accessible to solvent molecules) and potential readily accessible metal active sites, has been driven by both supramolecular host鈥揼uest recognition and coordinative assembly. The thermal behavior of native and nickel-containing crystals was studied by hot stage microscopy and differential scanning calorimetry. The decomposition temperatures of the multicomponent materials, 465鈥?70 掳C, are about 100 掳C higher than those of the single building blocks.