Continuous control of optical gaps in quasi-one-dimensional bromide-bridged platinum complexes by utilizing chemical pressure

Shohei Kumagai, Hiroaki Iguchi, Shinya Takaishi, Brian K. Breedlove, Masahiro Yamashita, Hiroyuki Matsuzaki, Hiroshi Okamoto, Kenichi Kato, Masaki Takata

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)

Abstract

The optical gap in a series of bromo-bridged platinum chain complexes, [Pt(en)2Br](Cn-Y)2·H2O (en = ethylenediamine; Cn-Y = dialkyl sulfosuccinate; n = the number of carbon atoms), was controlled by using chemical pressure. From the single-crystal structure, [Pt(en)2Br](C6-Y)2·H2O is in a mixed-valence state at 200 K. In addition, Pt-Pt distances decreased with an increase in n or with a decrease in the temperature. Continuous decreases in the optical gaps upon cooling were observed for n = 5, 7. The smallest gap of 1.20 eV was observed for n = 7 at 50 K. For n = 12, the complex was still in a mixed-valence state at 5 K, although the Pt-Pt distance was quite short. This is probably because of the energetic mismatch between 5dz2 orbitals of the Pt ions and 4pz orbitals of the Br ions.

Original languageEnglish
Pages (from-to)11764-11769
Number of pages6
JournalInorganic chemistry
Volume53
Issue number21
DOIs
Publication statusPublished - 2014 Nov 3

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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