Observation of the properties of a single unit of a limited CDW structure in a PtIIPtIV host-guest binary system based on a square-shaped complex

Eri Hirahara, Shinya Takaishi, Masahiro Yamashita

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1 Citation (Scopus)

Abstract

A macrocyclic tetranuclear platinum(II) complex [Pt(en)(4,4′bpy)] 4(NO3)8 (1-(NO3)8; en = ethylenediamine, 4,4′-bpy = 4,4′-bipyridine) and a mononuclear platinum(IV) complex [Pt(en)2Br2]Br2 (2-Br 2) formed two kinds of PtII/PtIV mixed valence assemblies when reacted: a discrete hostguest complex 1.2.Br10 (3) and an extended 1-D zigzag sheet 1.(2)3.Br8 (NO 3)6 (4). Single crystal X-ray analysis showed that the dimensions of the assemblies could be stoichiometrically controlled. Resonance Raman spectra suggested the presence of an intervalence interaction, which is typically observed for quasi-1-D halogen-bridged MII/MIV complexes. The intervalence interaction indicates the presence of an isolated {PtII-X-PtIV-X-PtII} moiety in the structure of 4. On the basis of electronic spectra and polarized reflectance measurements, we conclude that 4 exhibits intervalence charge transfer (IVCT) bands. A Kramers-Kronig transformation was carried out to obtain an optical conductivity spectrum, and two sub-bands corresponding to slightly different Pt II-PtIV distances were observed.

Original languageEnglish
Pages (from-to)1442-1450
Number of pages9
JournalChemistry - An Asian Journal
Volume4
Issue number9
DOIs
Publication statusPublished - 2009 Sep 1

Keywords

  • Charge transfer hostguest systems
  • Mixed valence
  • Platinum
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry

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