Achieving Reversible Sensing of Nitroxyl by Tuning the Ligand Environment of Azamacrocyclic Copper(II) Complexes

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• 作者：Sunghee Kim ; Mikael A. Minier ; Andrei Loas ; Sabine Becker ; Fang Wang ; Stephen J. Lippard
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：February 17, 2016
• 年：2016
• 卷：138
• 期：6
• 页码：1804-1807
• 全文大小：318K
• ISSN：1520-5126

文摘

To elucidate the factors that impart selectivity for nitroxyl (HNO) over nitric oxide (NO), thiols, and H₂S in metal-based fluorescent probes, we investigated five Cu(II)-cyclam (14-N₄) derivatives. Upon exposure to NO gas at pH 7, no changes occur in the UV–vis spectra of any of the complexes. Addition of Angeli’s salt to generate HNO promotes reduction of Cu(II) only in the case of [Cu^II(14-N₄-Ts)(OTf)₂], which has the most positive reduction potential of the series. To gain insight into the observed reactivity, we prepared the Cu(II) complex of the mixed thia/aza 14-N₂S₂ ligand. [Cu^II(14-N₂S₂)(OTf)₂] reacts reversibly with HNO at pH 7, although nonselectively over thiols and H₂S. The recurrent sensing of HNO uncovered with the study of Cu(II) azamacrocyclic complexes is a remarkable feature that opens the door for the design of a new generation of metal-based probes.