It's not just the size that matters: crystal engineering of lanthanide-based coordination polymers

Synthesis and characterization of Lewis base free coordination polymers of selected lanthanides are presented. For this purpose, the substituted Cot$^{TIPS}$ ligand (Cot$^{TIPS}$ = 1,4-bis-triisopropylsilyl-cyclo-octatetraendiide) was used to synthesize homoleptic, anionic multidecker compounds of the type [K{Ln$^{III}$(ɳ$^8$-Cot$^{TIPS}$)$_2$}]$_n$. Depending on the solvent used for crystallization and the ionic radii of the lanthanide cations, three different categories of one-dimensional heterobimetallic coordination polymers were obtained in the solid state. For the early lanthanides La and Ce a unique helical conformation was obtained by crystallization from toluene, while the ionic radius of Pr seems to be a turning point towards the crystallization of zigzag polymers. For Er a third structural motif, a trapezoidal wave polymer was observed. Additionally, the zigzag polymer for all compounds could be obtained by changing the solvent from toluene to Et$_2$O, reavealing a correlation between solid-state structure and ionic radii as well as solvent. While photoluminescence (PL) properties of Cot-lanthanide compounds are scarce, the La complexes show ligand centered green luminescence, whereas the Ce complexes reveal deep red emission origin from d–f transitions. ... mehrThe Er-compounds are single-molecule magnets, in which the magnetic relaxation of each Er ion occurs isolated from its neighbors at temperatures above 10 K, while below 9 K a strong antiferromagnetic coupling between the Er ions was seen.