Edwards Alyn C, Wagner Christoph, Geist Andreas, Burton Neil A, Sharrad Clint A, Adams Ralph W, Pritchard Robin G, Panak Petra J, Whitehead Roger C, Harwood Laurence M
School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Karlsruher Institut für Technologie (KIT-INE), Institut für Nukleare Entsorgung, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany and University of Heidelberg, Department of Physical Chemistry, Im Neuenheimer Feld 253, 69120, Germany.
Dalton Trans. 2016 Nov 15;45(45):18102-18112. doi: 10.1039/c6dt02474b.
The first examples of 4,7-disubstituted 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzo-triazin-3-yl)-1,10-phenanthroline (CyMe-BTPhen) ligands are reported herein. Evaluating the kinetics, selectivity and stoichiometry of actinide(iii) and lanthanide(iii) radiotracer extractions has provided a mechanistic insight into the extraction process. For the first time, it has been demonstrated that metal ion extraction kinetics can be modulated by backbone functionalisation and a promising new CHON compliant candidate ligand with enhanced metal ion extraction kinetics has been identified. The effects of 4,7-functionalisation on the equilibrium metal ion distribution ratios are far more pronounced than those of 5,6-functionalisation. The complexation of Cm(iii) with two of the functionalised ligands was investigated by TRLFS and, at equilibrium, species of 1 : 2 [M : L] stoichiometry were observed exclusively. A direct correlation between the E-E energy gap and metal ion extraction potential is reported, with DFT studies reaffirming experimental findings.
本文报道了4,7-二取代的2,9-双(5,5,8,8-四甲基-5,6,7,8-四氢-1,2,4-苯并三嗪-3-基)-1,10-菲咯啉（CyMe-BTPhen）配体的首个实例。对锕系元素(iii)和镧系元素(iii)放射性示踪剂萃取的动力学、选择性和化学计量进行评估，为萃取过程提供了机理见解。首次证明了金属离子萃取动力学可通过主链官能化进行调节，并确定了一种具有增强金属离子萃取动力学的、有前景的新型符合CHON要求的候选配体。4,7-官能化对平衡金属离子分配比的影响比5,6-官能化的影响更为显著。通过时间分辨激光荧光光谱法（TRLFS）研究了Cm(iii)与两种官能化配体的络合情况，在平衡时，仅观察到化学计量比为1 : 2 [M : L]的物种。报道了E-E能隙与金属离子萃取电位之间的直接相关性，密度泛函理论（DFT）研究再次证实了实验结果。
