Cerium(iv) complexes with guanidinate ligands: intense colors and anomalous electronic structures

A series of cerium(iv) mixed-ligand guanidinate-amide complexes, {[(Me₃Si)₂NC(N ⁱ Pr)₂] _x Ce^IV[N(SiMe₃)₂]_3-x }⁺ (x = 0-3), was prepared by chemical oxidation of the corresponding cerium(iii) complexes, where x = 1 and 2 represent novel complexes. The Ce(iv) complexes exhibited a range of intense colors, including red, black, cyan, and green. Notably, increasing the number of the guanidinate ligands from zero to three resulted in significant redshift of the absorption bands from 503 nm (2.48 eV) to 785 nm (1.58 eV) in THF. X-ray absorption near edge structure (XANES) spectra indicated increasing f occupancy (n _f) with more guanidinate ligands, and revealed the multiconfigurational ground states for all Ce(iv) complexes. Cyclic voltammetry experiments demonstrated less stabilization of the Ce(iv) oxidation state with more guanidinate ligands. Moreover, the Ce(iv) tris(guanidinate) complex exhibited temperature independent paramagnetism (TIP) arising from the small energy gap between the ground- and excited states with considerable magnetic moments. Computational analysis suggested that the origin of the low energy absorption bands was a charge transfer between guanidinate π orbitals that were close in energy to the unoccupied Ce 4f orbitals. However, the incorporation of sterically hindered guanidinate ligands inhibited optimal overlaps between Ce 5d and ligand N 2p orbitals. As a result, there was an overall decrease of ligand-to-metal donation and a less stabilized Ce(iv) oxidation state, while at the same time, more of the donated electron density ended up in the 4f shell. The results indicate that incorporating guanidinate ligands into Ce(iv) complexes gives rise to intense charge transfer bands and noteworthy electronic structures, providing insights into the stabilization of tetravalent lanthanide oxidation states.