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Ion‐Pairing Assemblies Based on Pentacyano‐Substituted Cyclopentadienide as a π‐Electronic Anion
Author(s) -
Bando Yuya,
Haketa Yohei,
Sakurai Tsuneaki,
Matsuda Wakana,
Seki Shu,
Takaya Hikaru,
Maeda Hiromitsu
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600686
Subject(s) - ion , pairing , electronic structure , crystallography , synchrotron , chemistry , charge (physics) , crystal structure , semiconductor , chemical physics , materials science , computational chemistry , condensed matter physics , physics , organic chemistry , optoelectronics , superconductivity , quantum mechanics , nuclear physics
Abstract Pentacyanocyclopentadienide (PCCp − ), a stable π‐electronic anion, provided various ion‐pairing assemblies in combination with various cations. PCCp − ‐based assemblies exist as single crystals and mesophases owing to interionic interactions with π‐electronic and aliphatic cations with a variety of geometries, substituents, and electronic structures. Single‐crystal X‐ray analysis revealed that PCCp − formed cation‐dependent arrangements with contributions from charge‐by‐charge and charge‐segregated assembly modes for ion pairs with π‐electronic and aliphatic cations, respectively. Furthermore, some aliphatic cations gave dimension‐controlled organized structures with PCCp − , as observed in the mesophases, for which synchrotron XRD analysis suggested the formation of charge‐segregated modes. Noncontact evaluation of conductivity for (C 12 H 25 ) 3 MeN + ⋅ PCCp − films revealed potential hole‐transporting properties, yielding a local‐scale hole mobility of 0.4 cm 2 V −1 s −1 at semiconductor–insulator interfaces.