Long aliphatic chain derivatives of trigonal lanthanide complexes

The trigonal lanthanide complexes LnL (H₃L = tris(((3-formyl-5-methylsalicylidene)amino)ethyl)amine) contain three pendant aldehyde groups and are known to react with primary amines. Reacting LnL (Ln = Yb, Lu) with 1-octadecylamine yields the novel aliphatic lanthanide complexes LnL¹⁸ (H₃L¹⁸ = tris(((3-(1-octadecylimine)-5-methylsalicylidene)amino)ethyl)amine) where the three aldehyde groups are transformed to 1-octadecylimine groups. Herein the syntheses, structural characterisation and magnetic properties of LnL¹⁸ are presented. The crystal structure of YbL¹⁸ shows that the reaction of YbL with 1-octadecylamine leads to only very subtle perturbations in the first coordination sphere of Yb(III), with the Yb(III) ion retaining its heptacoordination and similar bond lengths and angles to the ligand. The three octadecyl chains in each complex were found to direct crystal packing into lipophilic arrays of van der Waals interaction-driven hydrocarbon stacking. The static magnetic properties of YbL¹⁸ were compared to those of the non-derivatised complex YbL. The energy level splitting of the ²F_7/2 ground multiplet was found, by emission spectroscopy, to be very similar between the derivatised and non-derivatised complexes. A.c. magnetic susceptibility measurements on YbL¹⁸ and YbL diluted at 4.8% and 4.2% into the diamagnetic hosts LuL¹⁸ and LuL, respectively, revealed that the spin-lattice relaxation of both complexes is governed by a low temperature direct process and a high temperature Raman process. In the high temperature regime, the derivatised complex was also found to have faster spin-lattice relaxation, which is likely due to the increased number of phonons in the octadecyl chains.