One-dimensional Magnus-type platinum double salts

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.

Electrically Induced Mixed Valence Increases the Conductivity of Copper Helical Metallopolymers

“…As noted above, fully switched devices exhibit bulk conductivities of 2 S m –1 (Section 4.1, Supporting Information), but this value may be subject to future optimization. This conductivity is comparable to values reported for such one‐dimensional conductors as Krogmann [ 18 ] and Magnus salts, [ 19,22 ] the conductivity of which has been measured on single crystals. Our study, in contrast, probed the bulk behavior of relatively disordered, solution‐processed films.…”

“…[12] To this end, systems that contain linear chains of metal ions have been reported. [2,6,[13][14][15][16][17][18][19][20][21][22][23][24][25] Of these, extended metal atom chains (EMACs) are molecules in which the metal ions in the chain are electronically coupled, permitting the development of novel nanoelectronic devices. [14][15][16]24] The oxidation state of the metal ions in these materials has a critical impact on the electrical conductivity, with mixed-valence along the array creating a delocalized electronic system.…”

“…[ 14–16,24 ] The oxidation state of the metal ions in these materials has a critical impact on the electrical conductivity, with mixed‐valence along the array creating a delocalized electronic system. [ 15,16,22 ] While these previous works have investigated the impact of native mixed‐valence on the electronic properties, however, external control of the oxidation state remains to be explored, and exploited, in functional devices.…”

Electrically-Induced Mixed Valence Causes Resistive Switching in Copper Helical Metallopolymers

“…An appealing approach to create ordered structures at the nanoscale is to place the metal centres in direct communication with each other. To this end, systems that contain linear chains of metal ions have been reported 2,6,[20][21][22][23][24][12][13][14][15][16][17][18][19] . Of these, extended metal atom chains (EMACs) are molecules in which the metal ions in the chain are electronically coupled, permitting the development of novel nanoelectronic devices 18,[21][22][23] .…”

“…Of these, extended metal atom chains (EMACs) are molecules in which the metal ions in the chain are electronically coupled, permitting the development of novel nanoelectronic devices 18,[21][22][23] . The oxidation state of the metal ions in these materials has a critical impact on the electrical conductivity, with mixedvalence along the array creating a delocalized electronic system 16,22,23 . While these previous works have investigated the impact of native mixed-valence on the electronic properties, however, the external control of the oxidation state remains to be explored, and exploited in functional devices.…”