期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 142, 期 31, 页码 13500-13506出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c05217
关键词
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资金
- Academic Integration grant program at Cornell University
- College of Arts and Sciences at Cornell University
- National Institute of Biomedical Imaging and Bioengineering of the National Institutes of Health [R21EB027282]
- Cottrell Research Scholar Award from the Research Corporation for Science Advancement
- U.S. National Science Foundation [CHE-1531632]
Lanthanides (Ln(3+)) are critical materials used for many important applications, often in the form of coordination compounds. Tuning the thermodynamic stability of these compounds is a general concern, which is not readily achieved due to the similar coordination chemistry of lanthanides. Herein, we report two 18-membered macrocyclic ligands called macrodipa and macrotripa that show for the first time a dual selectivity toward both the light, large Ln(3+) ions and the heavy, small Ln(3+ )ions, as determined by potentiometric titrations. The lanthanide complexes of these ligands were investigated by NMR spectroscopy and X-ray crystallography, which revealed the occurrence of a significant conformational toggle between a 10-coordinate Conformation A and an 8-coordinate Conformation B that accommodates Ln(3+) ions of different sizes. The origin of this selectivity pattern was further supported by density functional theory (DFT) calculations, which show the complementary effects of ligand strain energy and metal-ligand binding energy that contribute to this conformational switch. This work demonstrates how novel ligand design strategies can be applied to tune the selectivity pattern for the Ln(3+)ions.
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