Ross Dolores L, Jasniewski Andrew J, Ziller Joseph W, Bominaar Emile L, Hendrich Michael P, Borovik A S
Department of Chemistry, 1102 Natural Science II, University of California, Irvine, California 92697, United States.
Department of Molecular Biology and Biochemistry, University of California, Irvine, California 92697, United States.
J Am Chem Soc. 2024 Jan 10;146(1):500-513. doi: 10.1021/jacs.3c09983. Epub 2023 Dec 27.
The exchange coupling of electron spins can strongly influence the properties of chemical species. The regulation of this type of electronic coupling has been explored within complexes that have multiple metal ions but to a lesser extent in complexes that pair a redox-active ligand with a single metal ion. To bridge this gap, we investigated the interplay among the structural and magnetic properties of mononuclear Cu complexes and exchange coupling between a Cu center and a redox-active ligand over three oxidation states. The computational analysis of the structural properties established a relationship between the complexes' magnetic properties and a bonding interaction involving a d orbital of the Cu ion and π orbital of the redox-active ligand that are close in energy. The additional bonding interaction affects the geometry around the Cu center and was found to be influenced by intramolecular H-bonds introduced by the external ligands. The ability to synthetically tune the d-π interactions using H-bonds illustrates a new type of control over the structural and magnetic properties of metal complexes.
电子自旋的交换耦合能够强烈影响化学物种的性质。在含有多个金属离子的配合物中，这类电子耦合的调控已得到研究，但在将氧化还原活性配体与单个金属离子配对的配合物中，相关研究较少。为填补这一空白，我们研究了单核铜配合物的结构和磁性之间的相互作用，以及铜中心与氧化还原活性配体在三种氧化态下的交换耦合。对结构性质的计算分析确定了配合物的磁性与一种键合相互作用之间的关系，该键合相互作用涉及能量相近的铜离子的d轨道和氧化还原活性配体的π轨道。额外的键合相互作用影响了铜中心周围的几何结构，并且发现它受外部配体引入的分子内氢键的影响。利用氢键对d-π相互作用进行合成调控的能力，说明了对金属配合物的结构和磁性进行新型控制的方法。
