Adewuyi Joseph A, Ung Gaël
Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, United States.
J Am Chem Soc. 2024 Mar 13;146(10):7097-7104. doi: 10.1021/jacs.4c01165. Epub 2024 Feb 27.
High quantum yield and circularly polarized luminescence (CPL) brightness values are reported from Shibasaki-type erbium complexes supported by a perfluorinated Binol ligand (FBinol). The total fluorination of the ligand circumvents nonradiative quenching from C-H vibrations and leads to quantum yields of up to 11% and CPL brightness values of up to 317 M cm (a 19- and 6-fold increase, respectively, compared to (Binol)ErNa). These values are the highest values for any molecular erbium complex to date, making them comparable to Yb emitters. A series of fluorinated Shibasaki-type complexes are synthesized by varying the alkali metal (K, Na, Li) in the secondary coordination sphere, leading to unexpected structural differences. NMR (F, Li) and chiroptical spectroscopy analyses provide insights into their structural geometry. With much improved quantum yields and CPL brightness values, we provide synthetic design principles toward other practical candidates for use in quantum communication technologies.
据报道，由全氟联萘配体（FBinol）支撑的柴崎型铒配合物具有高量子产率和圆偏振发光（CPL）亮度值。配体的全氟化避免了C-H振动引起的非辐射猝灭，导致量子产率高达11%，CPL亮度值高达317 M cm（与（联萘酚）ErNa相比，分别提高了19倍和6倍）。这些值是迄今为止任何分子铒配合物的最高值，使其与镱发光体相当。通过改变二级配位球中的碱金属（K、Na、Li）合成了一系列氟化柴崎型配合物，导致了意想不到的结构差异。核磁共振（F、Li）和手性光谱分析为其结构几何提供了见解。随着量子产率和CPL亮度值的大幅提高，我们为量子通信技术中其他实用候选物提供了合成设计原则。
