A new strategy for inducing dipole moments in charge-transfer complexes: Introduction of asymmetry into axially ligated iron phthalocyanines

Masaki Matsuda, Sayaka Iwamura, Yumi Hamada, Hiroko Ohishi, Miki Nishi, Yoshio Nogami, Mitsuo Ikeda, Akinori Kanda, Yusuke Funasako, Tomoyuki Mochida, Akiko Nakao, Noriaki Hanasaki

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)11800-11805
Number of pages6
JournalDalton Transactions
Volume46
Issue number35
DOIs
Publication statusPublished - 2017

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Dielectric relaxation
Dipole moment
Charge transfer
Iron
Activation energy
Crystal structure
Ligands
Atoms
Crystals
iron phthalocyanine
tetraphenylphosphonium
phthalocyanine

ASJC Scopus subject areas

  • Inorganic Chemistry

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A new strategy for inducing dipole moments in charge-transfer complexes : Introduction of asymmetry into axially ligated iron phthalocyanines. / Matsuda, Masaki; Iwamura, Sayaka; Hamada, Yumi; Ohishi, Hiroko; Nishi, Miki; Nogami, Yoshio; Ikeda, Mitsuo; Kanda, Akinori; Funasako, Yusuke; Mochida, Tomoyuki; Nakao, Akiko; Hanasaki, Noriaki.

In: Dalton Transactions, Vol. 46, No. 35, 2017, p. 11800-11805.

Research output: Contribution to journalArticle

Matsuda, M, Iwamura, S, Hamada, Y, Ohishi, H, Nishi, M, Nogami, Y, Ikeda, M, Kanda, A, Funasako, Y, Mochida, T, Nakao, A & Hanasaki, N 2017, 'A new strategy for inducing dipole moments in charge-transfer complexes: Introduction of asymmetry into axially ligated iron phthalocyanines', Dalton Transactions, vol. 46, no. 35, pp. 11800-11805. https://doi.org/10.1039/c7dt02605f
Matsuda, Masaki ; Iwamura, Sayaka ; Hamada, Yumi ; Ohishi, Hiroko ; Nishi, Miki ; Nogami, Yoshio ; Ikeda, Mitsuo ; Kanda, Akinori ; Funasako, Yusuke ; Mochida, Tomoyuki ; Nakao, Akiko ; Hanasaki, Noriaki. / A new strategy for inducing dipole moments in charge-transfer complexes : Introduction of asymmetry into axially ligated iron phthalocyanines. In: Dalton Transactions. 2017 ; Vol. 46, No. 35. pp. 11800-11805.
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