Jump to main content
Jump to site search

Issue 23, 2014
Previous Article Next Article

Predominance of covalency in water-vapor-responsive MMX-type chain complexes revealed by 129I Mössbauer spectroscopy

Author affiliations

Abstract

129I Mössbauer spectroscopy was applied to water-vapor-responsive MMX-type quasi-one-dimensional iodide-bridged Pt complexes (MMX chains) in order to investigate their electronic state quantitatively. Two sets of octuplets observed in K2(H3NC3H6NH3)[Pt2(pop)4I]·4H2O (2·4H2O) and one octuplet observed in K2(cis-H3NCH2CH[double bond, length as m-dash]CHCH2NH3)[Pt2(pop)4I]·4H2O (1·4H2O) and dehydrated complexes (1 and 2) indicate a unique alternating charge-polarization + charge-density-wave (ACP + CDW) electronic state and a charge-density-wave (CDW) electronic state, respectively. These spectra correspond to their crystal structure and the change of electronic states upon dehydration. Since these complexes consist of an alternating array of positively charged and negatively charged layers, the charge on the iodide ion (ρIS) was discussed on the basis of the isomer shift (IS). The ρIS of the water-vapor-responsive MMX chains was mainly −0.13 to −0.21, which are the smallest of all MMX chains reported so far. Hence, it indicates that the negative charge on the iodide ion is strongly donated to the Pt ion in these complexes. This covalent interaction predominates in the ACP + CDW state as well as in the CDW state. Therefore, the ACP + CDW state is in fact the CDW state with the ACP-type lattice distortion. Because the ρIS became smaller with the decreasing Pt–I–Pt distance, it can be concluded that the covalent interaction plays an important role in determining the electronic states of the MMX chains with pop (= P2H2O52–) ligands.

Graphical abstract: Predominance of covalency in water-vapor-responsive MMX-type chain complexes revealed by 129I Mössbauer spectroscopy

Back to tab navigation
Please wait while Download options loads

Supplementary files

Publication details

The article was received on 28 Feb 2014, accepted on 08 Apr 2014, published on 08 Apr 2014 and first published online on 08 Apr 2014


Article type: Paper
DOI: 10.1039/C4DT00627E
Citation: Dalton Trans., 2014,43, 8767-8773
  •   Request permissions

    Predominance of covalency in water-vapor-responsive MMX-type chain complexes revealed by 129I Mössbauer spectroscopy

    H. Iguchi, S. Kitao, M. Seto, S. Takaishi and M. Yamashita, Dalton Trans., 2014, 43, 8767
    DOI: 10.1039/C4DT00627E

Search articles by author