Abstract
Independently stacked positively and negatively charged π-electronic systems in charge-segregated columnar structures are desired for electronic properties derived from their electron-deficient and -rich assembling states, respectively. An expanded π-electronic cation, benzoporphyrin Au(III) complex, was synthesized as the component of ion pairs in combination with counteranions. In contrast to benzoporphyrin, which is known for its insolubility in organic solvents, the ion pairs with bulky anions in this study are soluble in common organic solvents. The ion pairs formed charge-segregated assemblies as two pseudo-polymorphs of single-crystal and less-crystalline (LeC) states based on the stacking of the benzoporphyrin Au(III) complex. XRD and solid-state NMR measurements, along with molecular dynamics (MD) simulation, revealed that the LeC states were formed by a less-ordered arrangement of constituting ions induced by bulky counteranions. The electric conductivity properties were observed in the single-crystal and LeC charge-segregated assemblies.