Diverse Crystal Structures of Ion Pairs Consisting of Oxaporphyrinium Cations and Pentacyanocyclopentadienide

Abstract

Intermolecular interaction is the key to controlling the crystal packing structure of π-conjugated systems. Here we synthesized ion pairs consisting of various oxaporphyrinium cations and pentacyanocyclopentadienide. Their crystal packing structures differed depending on the central metals of the oxaporphyrinium cation. Energy decomposition analysis clarified that dispersion and electrostatic forces played a critical role in determining the packing structures.

π-Electronic ion pairs: building blocks for supramolecular nanoarchitectonics viaiπ–iπ interactions

“…55 Similarly, in the PCCp À ion pair with oxaporphyrin Ni II complex 52a + , the constituent ions form the respective stacked dimers with interplanar distances of 3.31 and 3.28 Å, respectively. 84 Besides, PCCp À ion pairs of free-base 17b + and Zn II complex 52b + form one-by-one charge-by-charge assemblies. In contrast to the almost parallel arrangement observed in 17b + and PCCp À , in the ion pair 52b + -PCCp À , the components are not arranged in parallel owing to the coordination of PCCp À CN to the Zn II centre (Fig.…”