Lanthanide complexes of the chiral hexaaza macrocycle and its meso-type isomer: solvent-controlled helicity inversion

Lanthanide(III) complexes of the enantiopure chiral hexaaza tetraamine macrocycle L, 2(R),7(R),18(R),23(R)-1,8,15,17,24,31-hexaazatricyclo[25.3.1.1.0.0]-dotriaconta-10,12,14,26,28,30-hexaene, as well as of its meso-type 2(R),7(R),18(S),23(S)-isomeric macrocycle L1, have been synthesized and characterized by spectroscopic methods. The 2D NMR spectra confirm the identity of these complexes and indicate C2 symmetry of the [LnL]3+ and Cs symmetry of the [LnL1]3+ complexes. The crystal structures of the [PrL(NO3)(H2O)2](NO3)2, [EuL(NO3)(H2O)2](NO3)2, [DyL(NO3)2]2[Dy(NO3)5] x 5CH3CN, [YbL(NO3)2]2[Yb(NO3)5] x 5CH3CN, [YbL(H2O)2](NO3)3 x H2O, and [EuL1(NO3)(H2O)2]0.52[EuL1(NO3)2]0.48(NO3)1.52 x 0.48H2O complexes have been determined by single-crystal X-ray diffraction. In all complexes, the lanthanide(III) ions are coordinated by six nitrogen atoms of the macrocycle L or L1, but for each type of complex, the conformation of the macrocycle and the axial ligation are different. The crystallographic, NMR, and CD data show that the [YbL]3+ complex exists in two stable forms. Both forms of the Yb(III) complex have been isolated, and their interconversion was studied in various solvents. The two forms of [YbL]3+ complex correspond to two diastereomers of ligand L, which differ in the sense of the helical twist and the configuration at the stereogenic amine nitrogen atoms. In one of the stereoisomers, the macrocycle L of (RRRR) configuration at the stereogenic cyclohexane carbon atoms adopts the (RSRS) configuration at the amine nitrogen atoms, while in the other stereoisomer, the macrocycle L of (RRRR) configuration at the stereogenic cyclohexane carbon atoms adopts the (SSSS) configuration at the amine nitrogen atoms. The (RRRR)(RSRS) isomer is quantitatively converting to the (RRRR)(SSSS) isomer in water solution, while the reverse process is observed for an acetonitrile solution, thus representing the rare case of helicity inversion controlled by the solvent.