One-dimensional Magnus-type platinum double salts.

Christopher H Hendon,Ken Sakai,Aron Walsh,Yosuke Konno,Hiroshi Kitagawa,Takashi Kajiwara,Norinobu Akiyama,Tasuku Ito

doi:10.1038/ncomms11950

Abstract

Interest in platinum-chain complexes arose from their unusual oxidation states and physical properties. Despite their compositional diversity, isolation of crystalline chains has remained challenging. Here we report a simple crystallization technique that yields a series of dimer-based 1D platinum chains. The colour of the Pt2+ compounds can be switched between yellow, orange and blue. Spontaneous oxidation in air is used to form black Pt2.33+ needles. The loss of one electron per double salt results in a metallic state, as supported by quantum chemical calculations, and displays conductivity of 11 S cm−1 at room temperature. This behaviour may open up a new avenue for controllable platinum chemistry.

Highlights

Interest in platinum-chain complexes arose from their unusual oxidation states and physical properties
Unlike the colourful Pt-chain complexes, black compounds are interesting for electronic applications, owing to their potentially high conductivity and strong optical absorption
The unpaired valence electrons are delocalized along the Pt chain (Fig. 4a) in agreement with its diamagnetic character evidenced by electron spin resonance spectroscopy

Summary

Introduction

Interest in platinum-chain complexes arose from their unusual oxidation states and physical properties. Despite their compositional diversity, isolation of crystalline chains has remained challenging. In 2006, Bredas and colleagues[13] revisited Magnus’ green salt ([Pt(NH3)4][PtCl4]) and showed that the material possesses interesting band properties for conductive applications, owing to the Pt–Pt interactions; later, Drew et al.[14] harnessed highly coloured Pt-chain complexes as selective photochromic sensors. In the past half century, a variety of highly coloured platinum complexes[18] have been isolated including red[19], orange[20], yellow[21,22], green[23,24] and blue[25]

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Results

Conclusion