Coates, CS;
Makepeace, JW;
Seel, AG;
Baise, M;
Slater, B;
Goodwin, AL;
(2018)
Synthesis, PtS-type structure, and anomalous mechanics of the Cd(CN)₂ precursor Cd(NH₃)₂[Cd(CN)₄].
Dalton Transactions
, 47
(21)
pp. 7263-7271.
10.1039/c8dt01128a.
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Abstract
We report the nonaqueous synthesis of Cd(CN)₂ by oxidation of cadmium metal with Hg(CN)₂ in liquid ammonia. The reaction proceeds via an intermediate of composition Cd(NH₃)₂[Cd(CN)₄], which converts to Cd(CN)₂ on prolonged heating. Powder X-ray diffraction measurements allow us to determine the crystal structure of the previously-unreported Cd(NH₃)₂[Cd(CN)₄], which we find to adopt a twofold interpenetrating PtS topology. We discuss the effect of partial oxidation on the Cd/Hg composition of this intermediate, as well as its implications for the reconstructive nature of the deammination process. Variable-temperature X-ray diffraction measurements allow us to characterise the anisotropic negative thermal expansion (NTE) behaviour of Cd(NH₃)₂[Cd(CN)₄] together with the effect of Cd/Hg substitution; ab initio density functional theory (DFT) calculations reveal a similarly anomalous mechanical response in the form of both negative linear compressibility (NLC) and negative Poisson's ratios.
| Type: | Article |
|---|---|
| Title: | Synthesis, PtS-type structure, and anomalous mechanics of the Cd(CN)₂ precursor Cd(NH₃)₂[Cd(CN)₄] |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/c8dt01128a |
| Publisher version: | https://doi.org/10.1039/C8DT01128A |
| Language: | English |
| Additional information: | This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10074037 |
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