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

Abstract

Abstract 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 [Ln 3 Ti(HSA) 6 (SA) 4 (H 2 O)] − ({Ln 3 Ti‐SA}, H 2 SA=salicylic acid, Ln=Eu/Gd) to form new building blocks {Ln 3 Ti x ‐MSA} (H 2 MSA=5‐methoxysalicylic acid, x =1, 2, 3) by constructing [Ti(MSA) 3 ] 2− units. The obtained {Ln 3 Ti x ‐MSA} can further assemble into a chiral Ln 22 Ti 14 ring with the formulae [Eu 22 Ti 14 (MSA) 48 (HMSA) 22 (CH 3 COO) 4 (H 2 O) 10 (iPrOH)] and [Gd 22 Ti 14 (MSA) 46 (HMSA) 26 (CH 3 COO) 4 (H 2 O) 8 ]. Parallel experiments without Ti 4+ 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.