Ionic liquid induced spontaneous symmetry breaking: emergence of predominant handedness during the self-assembly of tetrakis(4-sulfonatophenyl)porphyrin (TPPS) with achiral ionic liquid

The self-assembly and supramolecular chirality of a dianionic tetrakis(4-sulfonatophenyl) porphyrin (TPPS) in the presence of ionic liquids, 1-alkyl-3-methylimidazolium tetrafluoroborate (alkyl = C-2, C-4 or C-6, abbreviated as C(2)mimBF(4), C(4)mimBF(4) and C(6)mimBF(4), respectively), have been investigated. It has been confirmed that mimBF(4) ionic liquids significantly promoted the J-aggregation of TPPS and the alkyl chain length in the imidazolium cation was closely related to the TPPS aggregation, the inducing ability of which decreased in the order of C-2, C-4 or C-6 in side chain. Interestingly, the formed TPPS assemblies with the ionic liquids showed supramolecular chirality although both TPPS and ionic liquids are achiral. It was found that the supramolecular chirality of the TPPS/IL system always appeared after the formation of the J aggregate. The dynamic process of the emergence of the handedness in the initial achiral system was monitored by the time-dependent CD spectra. A mechanism for the transformation of the conventional J-aggregate to the chiral J-aggregate was proposed. The work will lead to a deeper understanding of the chiral symmetry breaking in the supramolecular system.