TY - JOUR
T1 - A new strategy for inducing dipole moments in charge-transfer complexes
T2 - Introduction of asymmetry into axially ligated iron phthalocyanines
AU - Matsuda, Masaki
AU - Iwamura, Sayaka
AU - Hamada, Yumi
AU - Ohishi, Hiroko
AU - Nishi, Miki
AU - Nogami, Yoshio
AU - Ikeda, Mitsuo
AU - Kanda, Akinori
AU - Funasako, Yusuke
AU - Mochida, Tomoyuki
AU - Nakao, Akiko
AU - Hanasaki, Noriaki
N1 - Funding Information:
This study was supported in part by a Grant-in-Aid for Scientific Research (C) (no. 25410097 and 16 K05752) from the Japan Society for the Promotion of Science and a Grant-in-Aid for Scientific Research on Innovative Areas “New Frontier of Materials Science Opened by Molecular Degrees of Freedom” (no. 23110720) from the Ministry of Education, Culture, Sports, Science and Technology. The authors thank Dr H. Seo (RIKEN) for his fruitful discussion.
Publisher Copyright:
© 2017 The Royal Society of Chemistry.
PY - 2017
Y1 - 2017
N2 - Introduction of asymmetry into charge-transfer complexes composed of axially ligated iron phthalocyanines was achieved. In the obtained crystals of TPP[FeIII(Pc)(CN)Cl]2, TPP[FeIII(Pc)(CN)Br]2, and TPP[FeIII(Pc)BrCl]2 (TPP = tetraphenylphosphonium and Pc = phthalocyanine), the axial positions of the iron atoms were occupied by 50/50 ratios of the ligands CN/Cl, CN/Br, and Br/Cl, respectively. The crystal structures of the obtained CT complexes were isostructural to those composed of the symmetric analogues of the type [FeIII(Pc)L2] (L = CN, Cl or Br); the [FeIII(Pc)LL′] units formed regular one-dimensional chains along the c-axis following the symmetry of the P42/n space group. Despite forming similar regular chains to the symmetric systems, the electrical resistivities and activation energies were enhanced in the obtained CT complexes compared to those in symmetric systems, indicating that the charge-ordered states were stabilised by the introduction of asymmetry. More specifically, the dielectric relaxation behaviour of the inhomogeneous disordered TPP[FeIII(Pc)(CN)Cl]2 probably suggests that a dipole moment was induced in this material.
AB - Introduction of asymmetry into charge-transfer complexes composed of axially ligated iron phthalocyanines was achieved. In the obtained crystals of TPP[FeIII(Pc)(CN)Cl]2, TPP[FeIII(Pc)(CN)Br]2, and TPP[FeIII(Pc)BrCl]2 (TPP = tetraphenylphosphonium and Pc = phthalocyanine), the axial positions of the iron atoms were occupied by 50/50 ratios of the ligands CN/Cl, CN/Br, and Br/Cl, respectively. The crystal structures of the obtained CT complexes were isostructural to those composed of the symmetric analogues of the type [FeIII(Pc)L2] (L = CN, Cl or Br); the [FeIII(Pc)LL′] units formed regular one-dimensional chains along the c-axis following the symmetry of the P42/n space group. Despite forming similar regular chains to the symmetric systems, the electrical resistivities and activation energies were enhanced in the obtained CT complexes compared to those in symmetric systems, indicating that the charge-ordered states were stabilised by the introduction of asymmetry. More specifically, the dielectric relaxation behaviour of the inhomogeneous disordered TPP[FeIII(Pc)(CN)Cl]2 probably suggests that a dipole moment was induced in this material.
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U2 - 10.1039/c7dt02605f
DO - 10.1039/c7dt02605f
M3 - Article
C2 - 28831481
AN - SCOPUS:85029314100
SN - 1477-9226
VL - 46
SP - 11800
EP - 11805
JO - Dalton Transactions
JF - Dalton Transactions
IS - 35
ER -