Ion-Pairing Assemblies Based on Pentacyano-Substituted Cyclopentadienide as a π-Electronic Anion.
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 (C12 H25 )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.
Department of Applied Chemistry, College of Life Sciences and College of Pharmaceutical Sciences, Ritsumeikan University, Kusatsu, 525-8577, Japan.
Yuya
Y
Bando
Department of Applied Chemistry, College of Life Sciences and College of Pharmaceutical Sciences, Ritsumeikan University, Kusatsu, 525-8577, Japan.
Yohei
Y
Haketa
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan.
Tsuneaki
T
Sakurai
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan.
Wakana
W
Matsuda
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Kyoto, 615-8510, Japan.
Shu
S
Seki
International Research Center for Elements Science, Institute for Chemical Research, Kyoto University, Uji, 611-0011, Japan.
Hikaru
H
Takaya
Department of Applied Chemistry, College of Life Sciences and College of Pharmaceutical Sciences, Ritsumeikan University, Kusatsu, 525-8577, Japan. maedahir@ph.ritsumei.ac.jp.
Hiromitsu
H
Maeda
crystal growth; ion pairs; liquid crystals; phase transitions; pi-electronic systems