Journal of the American Chemical Society
Journal of the American Chemical Society
5 years ago

Intraligand Charge Transfer Sensitization on Self-Assembled Europium Tetrahedral Cage Leads to Dual-Selective Luminescent Sensing toward Anion and Cation

Intraligand Charge Transfer Sensitization on Self-Assembled Europium Tetrahedral Cage Leads to Dual-Selective Luminescent Sensing toward Anion and Cation
Ke-Li Han, Li-Xuan Cai, Rui-Ling Zhang, Cui-Lian Liu, Jin-Tao Kong, Li-Peng Zhou, Chen-Sheng Lin, Qing-Fu Sun, Song-Qiu Yang
Luminescent supramolecular lanthanide edifices have many potential applications in biology, environments, and materials science. However, it is still a big challenge to improve the luminescent performance of multinuclear lanthanide assemblies in contrast to their mononuclear counterparts. Herein, we demonstrate that combination of intraligand charge transfer (ILCT) sensitization and coordination-driven self-assembly gives birth to bright EuIII tetrahedral cages with a record emission quantum yield of 23.1%. The ILCT sensitization mechanism has been unambiguously confirmed by both time-dependent density functional theory calculation and femtosecond transient absorption studies. Meanwhile, dual-responsive sensing toward both anions and cations has been demonstrated making use of the ILCT transition on the ligand. Without introduction of additional recognition units, high sensitivity and selectivity are revealed for the cage in both turn-off luminescent sensing toward I– and turn-on sensing toward Cu2+. This study offers important design principles for the future development of luminescent lanthanide molecular materials.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05157

DOI: 10.1021/jacs.7b05157

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