Bagha Hena, Hein Robert, Lim Jason Y C, Myers William K, Sambrook Mark R, Beer Paul D
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK.
CBR Division, Dstl Porton Down, Salisbury, SP4 0JQ, UK.
Dalton Trans. 2024 Jul 23;53(29):12338-12348. doi: 10.1039/d4dt01585a.
Combining the potency of non-covalent halogen bonding (XB) with metal ion coordination, the synthesis and characterisation of a series of hydrophilic XB tripodal Cu(II) metallo-receptors, strategically designed for tetrahedral anion guest binding and sensing in aqueous media is described. The reported metallo-hosts contain a tripodal -symmetric tris-iodotriazole XB donor anion recognition motif terminally functionalised with tri(ethylene glycol) and permethylated β-cyclodextrin functionalities to impart aqueous solubility. Optical UV-vis anion binding studies in combination with unprecedented quantitative EPR anion titration investigations reveal the XB Cu(II) metallo-receptors exhibit strong and selective phosphate recognition over a range of other monocharged anionic species in competitive aqueous solution containing 40% water, notably outperforming a hydrogen bonding (HB) Cu(II) metallo-receptor counterpart. Electrochemical studies demonstrate further the capability of the metallo-receptors to sense anions significant cathodic perturbations of the respective Cu(II)/Cu(I) redox couple.
将非共价卤素键合(XB)的效力与金属离子配位相结合,本文描述了一系列亲水性XB三脚架型Cu(II)金属受体的合成与表征,这些受体是经过精心设计的,用于在水性介质中对四面体阴离子客体进行结合和传感。所报道的金属主体包含一个三脚架对称的三碘三唑XB供体阴离子识别基序,末端用三(乙二醇)和全甲基化的β-环糊精官能团进行功能化,以赋予其水溶性。光学紫外-可见阴离子结合研究与前所未有的定量EPR阴离子滴定研究相结合,揭示了XB Cu(II)金属受体在含有40%水的竞争性水溶液中,对一系列其他单电荷阴离子物种表现出强且选择性的磷酸盐识别能力,明显优于氢键(HB)Cu(II)金属受体对应物。电化学研究进一步证明了金属受体传感阴离子的能力——相应的Cu(II)/Cu(I)氧化还原对发生显著的阴极扰动。