Binuclear catalytic sites attained in a controlled way with complementary and cooperative metal ion centers are highly relevant in the development of new or enhanced catalytic processes. Herein, binuclear sites carrying Fe(III), Cu(II), or Mn(III) metal ions with a polarized structure have been prepared using the ionic self-assembly of oppositely charged metalloporphyrins. Binary porphyrin structures (BIPOS) have been prepared based on metalloporphyrin cations carrying pyridinium or methylpyridinium groups in conjugation with metalloporphyrin anions carrying sulfonatophenyl groups. BIPOS carrying [cation/anion] tecton pairs of [Cu/Fe], [Fe/Cu], [Cu/Cu], [Fe/Fe], [Mn/Fe], [Fe/Mn], and [Mn/Mn] have been compared. Electrochemical interaction and enhanced catalytic behavior are noticeable for BIPOS [Fe/Cu], [Fe/Fe], and [Mn/Fe] carrying a Fe center and [less electronegative/more electronegative] metal ion centers in the [cation/anion] porphyrin ionic pairs. For high-performance BIPOS, cyclic voltammograms showed a greater separation of the cathodic and anodic peaks, within ΔE_p = 0.095–0.125 V, and the rate constants for the catalytic reduction of 4-nitrophenol were within k = 0.380–0.535 min^–1/mg of catalyst, significantly superior to the related individual metalloporphyrins. Inverse heterobimetallic [Cu/Fe] and [Fe/Mn] and the homometallic BIPOS [Cu/Cu] and [Mn/Mn] were significantly less active or inefficient. A [Fe/Cu] material could be reused in at least 5 catalytic cycles, maintaining catalytic activity; the best catalysts were also active in the reduction of nitrobenzene to aniline in mild conditions (visible light, 30 °C, 0.5 mol % catalyst), and an [Fe/Fe] catalyst showed 100% aniline yield after 2 h.

中文翻译：

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Cu（II）、Fe（III） 和 Mn（III） 卟啉离子结构中的极化双金属位点协同作用：硝基芳烃的电化学和催化加氢


以受控方式获得的双核催化位点与互补和合作的金属离子中心与开发新的或增强的催化过程高度相关。在此，使用带相反电荷的金属卟啉的离子自组装制备了携带具有极化结构的 Fe（III）、Cu（II） 或 Mn（III） 金属离子的双核位点。二元卟啉结构 （BIPOS） 是基于携带吡啶或甲基吡啶基团的金属卟啉阳离子与携带磺酰苯基团的金属卟啉阴离子共轭制备的。对携带 [Cu/Fe]、[Fe/Cu]、[Cu/Cu]、[Fe/Fe]、[Mn/Fe]、[Fe/Mn] 和 [Mn/Mn] 的 [阳离子/阴离子] 构造对的 BIPOS 进行了比较。对于 BIPOS [Fe/Cu]、[Fe/Fe] 和 [Mn/Fe] 在 [阳离子/阴离子] 卟啉离子对中携带 Fe 中心和 [电负性较低/电负性较高] 金属离子中心的 BIPOS [Fe/Cu]、[Fe/Fe] 和 [Mn/Fe] 的电化学相互作用和增强的催化行为是明显的。对于高性能 BIPOS，循环伏安图显示阴极峰和阳极峰的分离度更高，在 ΔE_p = 0.095–0.125 V 范围内，4-硝基苯酚催化还原的速率常数在 k = 0.380–0.535 min^–1/mg 催化剂范围内，明显优于相关的单个金属卟啉。逆异质双金属 [Cu/Fe] 和 [Fe/Mn] 以及同金属 BIPOS [Cu/Cu] 和 [Mn/Mn] 的活性或效率显著降低。一种 [Fe/Cu] 材料可以在至少 5 次催化循环中重复使用，同时保持催化活性;在温和条件下（可见光、30 °C、0.5 mol % 催化剂）将硝基苯还原为苯胺方面也具有活性，[Fe/Fe] 催化剂在 2 小时后显示 100% 的苯胺产率。