Department of Chemistry, Center for Biophysics and Quantitative Biology, and Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois, 61801, USA.
Dalton Trans. 2023 Jun 20;52(24):8376-8383. doi: 10.1039/d3dt01213a.
The geometries of copper coordination complexes are intricately related to their electron transfer capabilities, but the role of dynamics in these processes are not fully understood. We have previously reported CuCl(dpa), a complex exhibiting conformational fluxionality in its Cu state and rigidity upon oxidation to Cu. Here, we report the synthesis and characterization of [CuCl(dpa)], a complex exhibiting relative rigidity in its Cu state and structural dynamics upon oxidation to Cu. The dynamics of [CuCl(dpa)] were characterized X-ray diffraction, cyclic voltammetry, and EPR spectroscopy, where temperature-dependent interconversion between trigonal bipyramidal and square pyramidal geometries is observed. Coupling these solid and solution-state characterization data enabled assignment of the coordination geometries involved. Factors impacting these dynamics and their potential implications for electron transfer are discussed.
铜配位配合物的几何形状与其电子转移能力密切相关，但这些过程中动力学的作用尚未完全理解。我们之前报道了 CuCl(dpa)，一种在 Cu 状态下表现出构象弛豫性，而在氧化为 Cu 后则具有刚性的配合物。在这里，我们报告了[CuCl(dpa)]的合成和表征，该配合物在 Cu 状态下表现出相对刚性，而在氧化为 Cu 后则具有结构动力学。通过 X 射线衍射、循环伏安法和 EPR 光谱对[CuCl(dpa)]的动力学进行了表征，观察到在三角双锥和四方锥几何形状之间的温度依赖性互变。将这些固态和溶液态表征数据结合起来，可以对涉及的配位几何形状进行分配。讨论了影响这些动力学的因素及其对电子转移的潜在影响。
