Crystallographic and/or magnetic properties of neutral and cationic uranium(IV) sandwiched phthalocyanine complexes

Tabata, Chihiro; Watanabe, Hirohito*; Shirasaki, Kenji*; Sunaga, Ayaki*; Fukuda, Takamitsu*; Li, D.*; Yamamura, Tomoo*

Journal of Molecular Structure, 1277, p.134870_1 - 134870_8, 2023/04

https://doi.org/10.1016/j.molstruc.2022.134870

Neutral and cationic U(IV) sandwiched phthalocyanine (Pc) complexes were prepared. The neutral species, UPc, was obtained by the reaction of UCl] and phthalonitrile, and the [UPc][BF] crystals were grown by electrolysis. The structures of the complexes were determined crystallographically. A U(IV) ion has two electrons, which carry a magnetic moment localized at the U sites, making the complex magnetically active. The magnetic susceptibility measurement of UPc revealed that the system was paramagnetic with local magnetic moments down to 2 K, but these magnetic moments were suppressed, possibly by a ligand field effect. The paramagnetism was also confirmed by the magnetization curve without hysteresis. The cationic complex, [UPc][BF]] crystalized in a tetragonal structure with the space group , in which the UPc molecules stacked along the tetragonal -axis. The structure was similar to that of [LnPc][BF]], but with distinct disorder in the stacking plane. The stabilities of the crystal and molecular structures and the electronic configurations of UPc and [UPc][BF]] were evaluated via the calculations that included the multiconfigurational nature of the actinide element.