Chiroptical Nanofibers Generated from Achiral Metallophthalocyanines Induced by Diamine Homochirality

Optically active cofacial pi-pi phthalocyanine (Pc) stacked supramolecules were spontaneously and successfully generated from a mixture of four possible geometric isomers (C-4h, D-2h, C-2v, C-s) of achiral 4(5), 4'(5'),4 ''-(5 ''),4'''(5''')-tetracarboxymetallophthalocyanine (tcPcM; M=Ni, Cu) induced by an equimolar amount of inexpensive chiral diamine molecular sources in DMSO/CHCl3 mixed solvent under optimized conditions of the volume ratio of poor/good cosolvents, the molar ratio of chiral molecular diamine to tcPcM, the cavity metal of phthalocyanine, and the addition order of the amines. The sign and amplitude of circular dichroism spectra due to the supramolecular chirality and structure of the diamine molecules are impossible to remove by additions of the antipode diamine and trifluoroacetic acid. The chiral diamine was partly contained in nanofibers, and that retained in the solution can be recycled and reused to induce optically active tcPcM supramolecules.