Langmuir–Schaefer films of a set of achiral amphiphilic porphyrins: aggregation and supramolecular chirality

Abstract

A series of new achiral porphyrins with hydrophobic dodecyl chains and hydrophilic substituents were designed in order to clarify the relationship between molecular geometry and aggregation as well as the supramolecular chirality in Langmuir–Schaefer films. These achiral porphyrins have zero (TPPA0), one (TPPA1), two (TPPA2a, TPPA2b), three (TPPA3) and four (TPPA4) long hydrophobic chains, respectively. Most of the compounds showed good spreading behaviour on a water surface except TPPA4 and could be fabricated into LS films easily. Depending on the number of alkyl chains, the porphyrin derivatives showed different aggregation behaviour in the LS films. The transferred films were characterized by UV-vis, circular dichroism (CD) and FTIR spectroscopy, and atomic force microscopy (AFM). Interestingly, some of the porphyrin assemblies were found to be optically active in the LS films although the compounds themselves are achiral. TPPA3 showed a strong Cotton effect in the LS film and fiber-like morphology on mica surface. Weak supramolecular chirality was detected from the LS films of TPPA0, TPPA1 and TPPA4, but no Cotton effect was observed for the LS films of TPPA2a or TPPA2b. On the other hand, when the LS film of TPPA3 was dipped into hexane or exposed to HCl gas, which altered the hydrophobic effect among the dodecyl chains and destroyed the π–π interactions between the porphyrin macrocyclic rings, the CD signal decreased or disappeared. The different aggregation behaviour and supramolecular chirality in the films was suggested to be related to the molecular structure and subsequent packing in their organized molecular films.