Formation of helical J-aggregate of chiral thioether-derivatized phthalocyanine bound by palladium(II) at the toluene/water interface

A chiral thioether-substituted phthalocyanine ((2,3,9,10,16,17,23,24-octakis-l-phenylethylthiophthalocyaninato)magnesium(II) [MgPc(SEtPh)(8)]) has been synthesized, which can be bound by soft-metal ions such as palladium(II) ion. Aggregates formed from MgPe(SEtPh)(8) and Pd(II) in toluene and at the toluene/water interface were characterized by means of UV-vis absorption and circular dichroism (CD) spectrometries using centrifugal liquid-membrane (CLM) cell. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF/MS) and scanning electron microscope (SEM) were used as complementary techniques. The toluene solution of MgPc(SEtPh)(8) had no optical chirality. However, the addition of PdCl2 into the toluene solution of MgPc(SEtPh)(8) induced optical chirality, which indicated the formation of a twisted H-type dimer (face-to-face fashion) of MgPc(SEtPh)8 bound by four PdCl2 in the bulk toluene solution. On the other hand, in the toluene/water interface, helical J-aggregate (head-to-tail fashion) of MgPc(SEtPh)8 bound by PdCl2 was formed, in which one J-aggregate unit contained five 1:2 complexes of MgPc(SEtPh)(8)-Pd(II) on average. On the basis of the experimental results and the exciton theory for optical chirality, a possible mechanism for the chiral aggregation of MgPc(SEtPh)8-Pd(II) complexes at the interface was proposed. In the present study, we demonstrated a novel strategy for the design of helical phthalocyanine aggregates using the liquid/liquid interface as a template.