Evaluation of the Arrhenius behavior of n-dodecane radical cation (RH●+) reactivity with lanthanide ion-complexed N,N,N’,N’-tetraoctyl diglycolamide (TODGA)

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-12-20 DOI:10.1039/d4cp03633f

Maya H. Rogalski, Anh N Dang, Stephen Peter Mezyk

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引用次数: 0

Abstract

Temperature-dependent rate constants for the reaction of the n-dodecane radical cation (RH●+) with trivalent lanthanide ion-complexed N,N,N’,N’-tetraoctyl diglycolamide (TODGA) over the range 10-40oC have been determined by electron pulse radiolysis/transient absorption spectroscopy techniques. For the free ligand, an activation energy of Ea = 20.4 ± 0.7 kJ mol-1 and pre-exponential factor of ln(A) = 31.23 ± 0.27 were obtained, corresponding to a room-temperature rate constant of k = (9.94 ± 0.52) x 109 M-1 s-1. The RH●+ reactivity with La(TODGA)3(NO3)3, Nd(TODGA)3(NO3)3, Gd(TODGA)3(NO3)3, Yb(TODGA)3(NO3)3and Lu(TODGA)3(NO3)3 complexes had faster rate constants of k = (5.30 ± 0.51) x 1010, (4.23 ± 0.18) x 1010, (2.44 ± 0.13) x 1010, (1.68 ± 0.03) x 1010, and (9.1 ± 0.7) x 109 M-1 s-1, respectively. The corresponding Arrhenius activation energies determined for three (La, Gd, Lu) lanthanide-TODGA complexes showed consistent values of Ea = 35 ± 2.2, 35.3 ± 2.0, 33.5 ± 3.9 kJ mol-1, respectively. The similar and relatively large barrier energy suggests a common reaction mechanism involving electron abstraction from one of the coordinating nitrate anions, which is consistent for the previously reported decreased degradation of TODGA complexes under radiolytic environments.

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.