Modification of Multi‐Component Building Blocks for Assembling Giant Chiral Lanthanide‐Titanium Molecular Rings

Building blocks with multiple components are promising for the synthesis of complex molecular assemblies, but are rarely available. Herein, we report a modification procedure for a multi-component building block [Ln3 Ti(HSA)6 (SA)4 (H2 O)]- ({Ln3 Ti-SA}, H2 SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln3 Tix -MSA} (H2 MSA=5-methoxysalicylic acid, x=1, 2, 3) by constructing [Ti(MSA)3 ]2- units. The obtained {Ln3 Tix -MSA} can further assemble into a chiral Ln22 Ti14 ring with the formulae [Eu22 Ti14 (MSA)48 (HMSA)22 (CH3 COO)4 (H2 O)10 (iPrOH)] and [Gd22 Ti14 (MSA)46 (HMSA)26 (CH3 COO)4 (H2 O)8 ]. Parallel experiments without Ti4+ result in linear Ln chains. Detailed analysis shows that the [Ti(MSA)4 ]4- unit makes the originally variable Ln chains become available building blocks and the modified [Ti(MSA)3 ]2- further triggers interesting chiral-sorting behavior. Finally, the electronic adsorption and magneto-optic responses of these molecular rings are investigated.