Carbon NMR Titration Could Be More Informative for In-Situ Lanthanide Coordination Chemistry Investigation

In situ characterization of coordination species and their evolution are crucial for effective lanthanide separation and recycling. Current technical approaches often operate under constrained conditions, requiring complex equipment, experimental setups, and sometimes intricate data interpretation. Herein, we demonstrate that carbon NMR titrations offer a valuable approach for in situ coordination analysis of lanthanides, particularly for highly fused preorganized ligands that offer more NMR-active carbons than traditional proton NMR. Two representative ligands of both lipophilic and hydrophilic in nature were investigated, and the resulting carbon NMR titration data were analyzed. Comparisons with IR and single-crystal data showed that NMR provided insights not only into the evolution of coordination species but also into changes in the electron distribution during complex formation. Additionally, we discussed inconsistencies between atomic charge populations obtained from carbon NMR and those from Mulliken and Hirshfeld calculations. With advancements in NMR technology and the availability of higher-field NMR instruments, we believe NMR titrations will play an increasingly significant role in unravelling the complex solution coordination chemistry of f-block elements.