Pacific Northwest National Laboratory, 902 Battelle Boulevard, Richland, Washington 99354, United States.
Department of Fundamental Chemistry Institute of Chemistry, University of São Paulo, Av. Prof. Lineu Prestes 748, São Paulo 05508-000, Brazil.
Inorg Chem. 2023 Mar 27;62(12):4814-4822. doi: 10.1021/acs.inorgchem.2c03976. Epub 2023 Mar 15.
A novel actinide-containing coordination polymer, [Am(CO)(HO)Cl] (), has been synthesized and structurally characterized. The crystallographic analysis reveals that the structure is two-dimensional and comprised of pseudo-dimeric Am nodes that are bridged by oxalate ligands to form sheets. Each metal center is nine-coordinate, forming a distorted capped square antiprism geometry with a symmetry, and features bound oxalate, aqua, and chloro ligands. The Am-ligand bonds were probed computationally using the quantum theory of atoms in molecules nd natural localized molecular orbital approaches to investigate the underlying mechanisms and hybrid atomic orbital contributions therein. The analyses indicate that the bonds within are predominantly ionic and the 5f shell of the Am metal centers does not add a significant covalent contribution to the bonds. Our bonding assessment is supported by measurements on the optical properties of using diffuse reflectance and photoluminescence spectroscopies. The position of the principal absorption band at 507 nm (L ← F) is notable because it is consistent with previously reported americium oxalate complexes in solution, indicating similarities in the electronic structure and ionic bonding. Compound is an active phosphor, featuring strong bright-blue oxalate-based luminescence with no evidence of metal-centered emission.
一种新型含锕系元素的配位聚合物Am(CO)(HO)Cl已被合成并进行了结构表征。晶体学分析表明，该结构为二维结构，由假二聚锕节点通过草酸配体桥接形成层。每个金属中心为九配位，形成一个具有对称性的扭曲截角四方反棱柱几何形状，具有结合的草酸根、水合和氯配体。使用分子中的原子量子理论和自然局域分子轨道方法对 Am-配体键进行了计算研究，以探究其潜在机制和杂化原子轨道贡献。分析表明，内的键主要为离子键，Am 金属中心的 5f 壳层对键没有显著的共价贡献。我们的键评估得到了使用漫反射和光致发光光谱测量对光学性质的支持。主要吸收带位于 507nm（L←F）处的位置很重要，因为它与溶液中先前报道的镅草酸配合物一致，表明电子结构和离子键相似。化合物是一种活性磷光体，具有强烈的基于草酸的亮蓝色发光，没有金属中心发射的证据。
