Development of metal-organic framework (MOF)-B-12 system as new bio-inspired heterogeneous catalyst

作者：Xu, Jing; Shimakoshi, Hisashi^*; Hisaeda, Yoshio

来源：Journal of Organometallic Chemistry, 2015, 782: 89-95.

DOI：10.1016/j.jorganchem.2014.11.015

• Metal-organic framework
• Cation exchanging
• B-12
• Heterogeneous catalyst
• Recycle use

A novel bimetal complex {Za(4)Ru(2)(bpdc)(4) center dot 4C(2)NH(8)center dot 9DMF}(n) (1) (H(2)bpdc = 4,4'-biphenyldicarboxylic acid) was synthesized by the solvothermal method. The results of the X-ray crystallographic analysis revealed that 1 crystallizes in the orthorhombic Pna2(1) space group, which has a 3D 2-fold interpenetrated hex framework, with open channel sizes along the [010] direction of ca. 1.4 nm x 1.4 nm. The photosensitizer [Ru(bpy)(3)](2+) was adsorbed into the 1 to form Ru@MOF by cation exchanging. A cobalamin derivative (B-12), heptamethyl cobyrinate, was also effectively immobilized on Ru@MOF, and the resulting hybrid complex, B12Ru@MOF, exhibited a high reactivity for the dechlorination reaction of 1,1-bis(4chlorophenyl)-2,2,2-trichloroethane (DDT) under an N-2 atmosphere by visible light irradiation in the solid state. The catalysis of B12Ru@MOF can still reach more than a ca. 80% conversion after third recyclings. Furthermore, the heterogeneous catalyst, 1312 Ru @MOF, was useful for the cobalamindependent reaction, such as the 1,2-migration of the acetyl group.

• 出版日期2015-4-15
• 单位南京信息工程大学