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Rational design of materials with extreme negative compressibility: selective soft-mode frustration in KMn[Ag(CN)2]3.

Authors
Journal
Journal of the American Chemical Society
0002-7863
Publisher
American Chemical Society
Publication Date
Volume
134
Issue
10
Identifiers
DOI: 10.1021/ja204908m

Abstract

We show that KMn[Ag(CN)(2)](3) exhibits the strongest negative linear compressibility (NLC) effect over the largest pressure range yet observed. Variable pressure neutron powder diffraction measurements reveal that its crystal lattice expands along the c axis of its trigonal cell under increasing hydrostatic pressure, while contracting along the a axis. This corresponds to a "wine-rack"-like mechanism for NLC that we find also results in anisotropic negative thermal expansion (NTE) in the same material. Inclusion of extra-framework K(+) counterions has minimal effect on framework flexibility (and hence the magnitude of NTE/NLC) but selectively frustrates the soft phonon modes responsible for destroying NLC in the related material Ag(3)[Co(CN)(6)].

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