Porous Metalloporphyrinic Frameworks Constructed from Metal 5,10,15,20-Tetrakis(3,5-biscarboxylphenyl)porphyrin for Highly Efficient and Selective Catalytic Oxidation of Alkylbenzenes

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• 作者：Xiu-Li Yang ; Ming-Hua Xie ; Chao Zou ; Yabing He ; Banglin Chen ; Michael O鈥橩eeffe ; Chuan-De Wu
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：June 27, 2012
• 年：2012
• 卷：134
• 期：25
• 页码：10638-10645
• 全文大小：416K
• 年卷期：v.134,no.25(June 27, 2012)
• ISSN：1520-5126

文摘

We incorporate metal 5,10,15,20-tetrakis(3,5-biscarboxylphenyl)porphyrin (M-H₈OCPP), for the first time, into porous metal鈥搊rganic frameworks. The self-assembled porous metalloporphyrinic frameworks [Mn₅Cl₂(MnCl-OCPP)(DMF)₄(H₂O)₄]路2DMF路8CH₃COOH路14H₂O (ZJU-18; ZJU = Zhejiang University), [Mn₅Cl₂(Ni-OCPP)(H₂O)₈]路7DMF路6CH₃COOH路11H₂O (ZJU-19), and [Cd₅Cl₂(MnCl-OCPP)(H₂O)₆]路13DMF路2CH₃COOH路9H₂O (ZJU-20) are isostructural as revealed by their single X-ray crystal structures. The metalloporphyrin octacarboxylates (M-OCPP) (M = Mn^IIICl for ZJU-18 and ZJU-20, M = Ni^II for ZJU-19) are bridged by binuclear and trinuclear metal carboxylate secondary building units to form a 3-periodic, binodal, edge-transitive net with Reticular Chemistry Structure Resource symbol tbo with pore windows of about 11.5 脜 and pore cages about 21.3 脜 in diameter. The porous nature of these metalloporphyrinic frameworks is further established by sorption studies in which different substrates such as ethanol, acetonitrile, acetone, cyclohexane, benzene, toluene, ethylbenzene, and acetophenone can readily have access to the pores. Their catalytic activities for the oxidation of alkylbenzenes were examined at 65 掳C using tert-butyl hydroperoxide as the oxidant. The results indicate that ZJU-18 is much superior to ZJU-19, ZJU-20, and homogeneous molecular MnCl-Me₈OCPP, exhibiting highly efficient and selective oxidation of ethylbenzene to acetophenone in quantitative >99% yield and a turnover number of 8076 after 48 h.