Galley Shane S, Pattenaude Scott A, Gaggioli Carlo Alberto, Qiao Yusen, Sperling Joseph M, Zeller Matthias, Pakhira Srimanta, Mendoza-Cortes Jose L, Schelter Eric J, Albrecht-Schmitt Thomas E, Gagliardi Laura, Bart Suzanne C
Department of Chemistry and Biochemistry , Florida State University , Tallahassee , Florida 32306 , United States.
H.C. Brown Laboratory, Department of Chemistry , Purdue University , West Lafayette , Indiana 47907 , United States.
J Am Chem Soc. 2019 Feb 13;141(6):2356-2366. doi: 10.1021/jacs.8b10251. Epub 2019 Feb 4.
An isostructural family of f-element compounds (Ce, Nd, Sm, Gd; Am, Bk, Cf) of the redox-active dioxophenoxazine ligand (DOPO; DOPO = 2,4,6,8-tetra- tert-butyl-1-oxo-1 H-phenoxazin-9-olate) was prepared. This family, of the form M(DOPO), represents the first nonaqueous isostructural series, including the later actinides berkelium and californium. The lanthanide derivatives were fully characterized using H NMR spectroscopy and SQUID magnetometry, while all species were structurally characterized by X-ray crystallography and electronic absorption spectroscopy. In order to probe the electronic structure of this new family, CASSCF calculations were performed and revealed these systems to be largely ionic in contrast to previous studies, where berkelium and californium typically have a small degree of covalent character. To validate the zeroth order regular approximation (ZORA) method, the same CASSCF analysis using experimental structures versus UDFT-ZORA optimized structures does not exhibit sizable changes in bonding patterns. This shows that UDFT-ZORA combined with CASSCF could be a useful first approximation to predict and investigate the structure and electronic properties of actinides and lanthanides that are difficult to synthesize or characterize.
制备了氧化还原活性二氧代吩恶嗪配体（DOPO；DOPO = 2,4,6,8-四叔丁基-1-氧代-1H-吩恶嗪-9-醇盐）的f元素化合物（Ce、Nd、Sm、Gd；Am、Bk、Cf）的等结构系列。这个通式为M(DOPO)的系列代表了首个非水等结构系列，包括后锕系元素锫和锎。镧系衍生物通过1H NMR光谱和超导量子干涉仪磁力测定法进行了全面表征，而所有物种都通过X射线晶体学和电子吸收光谱进行了结构表征。为了探究这个新系列的电子结构，进行了完全活性空间自洽场（CASSCF）计算，结果表明与之前的研究相比，这些体系主要是离子性的，在之前的研究中，锫和锎通常具有较小程度的共价特征。为了验证零级正则近似（ZORA）方法，使用实验结构与UDFT-ZORA优化结构进行相同的CASSCF分析，结果显示键合模式没有显著变化。这表明UDFT-ZORA与CASSCF相结合可能是预测和研究难以合成或表征的锕系和镧系元素的结构和电子性质的一种有用的初步近似方法。
