Castro Kelly A D F, Silva Sandrina, Pereira Patrícia M R, Simões Mário M Q, Neves Maria da Graça P M S, Cavaleiro José A S, Wypych Fernando, Tomé João P C, Nakagaki Shirley
†Laboratório de Química Bioinorgânica e Catálise, Universidade Federal do Paraná (UFPR), CP 19081, CEP 81531-990, Curitiba, Paraná Brazil.
‡Department of Chemistry and QOPNA, University of Aveiro, 3810-193 Aveiro, Portugal.
Inorg Chem. 2015 May 4;54(9):4382-93. doi: 10.1021/acs.inorgchem.5b00196. Epub 2015 Apr 21.
This work employed [5,10,15,20-tetrakis(pentafluorophenyl)porphyrin] ([H2(TPPF20)], H2P1) as the platform to prepare a tetrasubstituted galactodendritic conjugate porphyrin (H2P3). After metalation with excess copper(II) acetate, H2P3 afforded a new solid porphyrin material, Cu4CuP3S. This work also assessed the ability of the copper(II) complex (CuP3) of H2P3 to coordinate with zinc(II) acetate, to yield the new material Zn4CuP3S. UV-visible, Fourier transform infrared, and electron paramagnetic resonance spectroscopies aided full characterization of the synthesized solids. (Z)-Cyclooctene epoxidation under heterogeneous conditions helped to evaluate the catalytic activity of Cu4CuP3S and Zn4CuP3S. The efficiency of Cu4CuP3S in the oxidation of another organic substrate, catechol, was also investigated. According to the results obtained in the heterogeneous process, Cu4CuP3S mimicked the activity of cytochrome P-450 and catecholase. In addition, Cu4CuP3S was reusable after recovery and reactivation. The data obtained herein were compared with the results achieved for the copper complex (CuP1) of [H2(TPPF20)] and for CuP3 under homogeneous conditions.
本研究以5,10,15,20-四（五氟苯基）卟啉为平台制备了一种四取代半乳糖树枝状共轭卟啉（H2P3）。用过量醋酸铜金属化后，H2P3得到了一种新型固体卟啉材料Cu4CuP3S。本研究还评估了H2P3的铜（II）配合物（CuP3）与醋酸锌配位生成新材料Zn4CuP3S的能力。紫外可见光谱、傅里叶变换红外光谱和电子顺磁共振光谱有助于对合成固体进行全面表征。非均相条件下的（Z）-环辛烯环氧化反应有助于评估Cu4CuP3S和Zn4CuP3S的催化活性。还研究了Cu4CuP3S对另一种有机底物邻苯二酚的氧化效率。根据非均相过程中获得的结果，Cu4CuP3S模拟了细胞色素P-450和儿茶酚酶的活性。此外，Cu4CuP3S回收再活化后可重复使用。本文获得的数据与[H2(TPPF20)]的铜配合物（CuP1）以及均相条件下CuP3的结果进行了比较。
