Bonding and Magnetic Trends in the [AnIII(DPA)3]3– Series Compared to the Ln(III) and An(IV) Analogues

• Published in: Inorganic chemistry 2023-10, Vol.62 (42), p.17254-17264
• Main Authors: Islam, Md. Ashraful, Berthon, Claude, Jung, Julie, Bolvin, Hélène
• Format: Article
• Language: English
• Subjects: Chemical Sciences; Coordination chemistry; or physical chemistry; Theoretical and
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.3c02482

The crystal field parameters are determined from first-principles calculations in the [AnIII(DPA)3]3– series, completing previous work on the [LnIII(DPA)3]3– and [AnIV(DPA)3]2– series. The crystal field strength parameter follows the Ln­(III) < An­(III) < An­(IV) trend. The parameters deduced at the orbital level decrease along the series, while J-mixing strongly impacts the many-electron parameters, especially for the Pu­(III) complex. We further compile the available data for the three series. In some aspects, An­(III) complexes are closer to Ln­(III) than to An­(IV) complexes with regard to the geometrical structure and bonding descriptors. At the beginning of the series, up to Pu­(III), there is a quantitative departure from the free ion, especially for the Pa­(III) complex. The magnetic properties of the actinides keep the trends of the lanthanides; in particular, the axial magnetic susceptibility follows Bleaney’s theory qualitatively.