RESUMEN
Recently, there has been increasing interest in the design of ligands that bind Mn2+ with high affinity and selectivity, but this remains a difficult challenge. It has been proposed that the cavity size of the binding pocket is a critical factor in most synthetic and biological examples of selective Mn2+ binding. Here, we use a bioinspired approach adapted from the hexahistidine binding site of the manganese-sequestering protein calprotectin to systematically study the effect of cavity size on Mn2+ and Zn2+ binding. We have designed a hexadentate, trisimidazole ligand whose cavity size can be tuned through peripheral modification of the steric bulk of the imidazole substituents. Conformational dynamics and redox potentials of the complexes are dependent on ligand steric bulk. Stability constants are consistent with the hypothesis that larger ligand cavities are relatively favorable for Mn2+ over Zn2+ , but this effect alone may not be sufficient to achieve Mn2+ selectivity.
RESUMEN
Metalloenzymes make extensive use of manganese centers for oxidative catalysis, including water oxidation; the need to develop improved synthetic catalysts for these processes has long motivated the development of bioinspired manganese complexes. Herein, we report a series of bpy-(imidazole)n (n = 1 or 2) (bpy = 2,2'-bipyridyl) ligands and their Mn2+ complexes. Four Mn2+ complexes are structurally characterized using single-crystal X-ray diffraction, revealing different tridentate and tetradentate ligand coordination modes. Cyclic voltammetry of the complexes is consistent with ligand-centered reductions and metal-centered oxidations, and UV-vis spectroscopy complemented by TD-DFT calculations shows primarily ligand-centered transitions with minor contributions from charge-transfer type transitions at higher energies. In solution, ESI-MS studies provide evidence for ligand reorganization, suggesting complex speciation behavior. The oxidation of the complexes in the presence of water is probed using cyclic voltammetry, but the low stability of the complexes in aqueous solution leads to decomposition and precludes their ultimate application as aqueous electrocatalysts. Possible reasons for the low stability and suggestions for improvement are discussed.
RESUMEN
(4-(Adamantan-1-yl)-1-(isopropyl)-1H-imidazol-2-yl)methanol was prepared through a five-step process starting from commercially available 1-acetyladamantane. Each step proceeded in moderate-to-excellent yields and the overall yield across five steps was 28%. The compound was identified and characterized by 1H and 13C{1H} NMR, high-resolution mass spectroscopy, and elemental analysis. This compound and its derivatives have the potential to be used as precursors to the synthesis of biomimetic chelating ligands.