A New Metal Carboxylate Framework Based on Porphyrin with Extended pi-Conjugation

作者：Matsunaga Satoshi^*; Endo Nanako; Mori Wasuke

来源：European Journal of Inorganic Chemistry, 2011, 2011(29): 4550-4557.

DOI：10.1002/ejic.201100660

• Microporous materials
• Zinc
• Metal-organic frameworks
• Porphyrinoids
• Carboxylate ligands

We have designed a new tetracarboxylporphyrin building block, ZnTCPEP-H-4, and used it in the construction of a novel porphyrin-based metal carboxylate framework, [Zn-4(mu(3)-OH)(2)(H2O)(2)(ZnTCPEP-H)(2)(DABCO)]center dot 2DMF center dot 10.5H(2)O (Zn-4 center dot ZnTCPEP center dot DABCO). The framework forms a 3D network linked by tetranuclear Zn cluster nodes {Zn-4(mu(3)-OH)(2)(H2O)(2)}, ZnTCPEP-H-4, and DABCO. The ZnTCPEP-H-4 building block exhibits extended pi-conjugation from the porphyrin core to the terminal carboxyl groups via ethynyl linkers attached to the porphyrin core. The Zn4 center dot ZnTCPEP center dot DABCO framework gives rise to a 3D porous structure containing open channels with cross sections of approximately 10 x 10 and 7 center dot 7 angstrom. It has a BET surface area of 461 m(2)/g and a Langmuir surface area of 581 m(2)/g. A hydrogen adsorption capacity of 0.86 wt.% was determined for Zn-4 center dot ZnTCPEP center dot DABCO at 77 K and 0.1 MPa.

• 出版日期2011-10