Rational Design of Materials with Extreme Negative Compressibility: Selective Soft-Mode Frustration in KMn[Ag(CN)2]3 | Zendy

Andrew B. Cairns | Zendy; Amber L. Thompson | Zendy; Matthew G. Tucker | Zendy; Julien Haines | Zendy; Andrew L. Goodwin | Zendy

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Rational Design of Materials with Extreme Negative Compressibility: Selective Soft-Mode Frustration in KMn[Ag(CN)₂]₃

Author(s) -

Andrew B. Cairns,

Amber L. Thompson,

Matthew G. Tucker,

Julien Haines,

Andrew L. Goodwin

Publication year - 2011

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja204908m

Subject(s) - chemistry , negative thermal expansion , compressibility , anisotropy , counterion , crystallography , hydrostatic pressure , dimer , neutron diffraction , condensed matter physics , stereochemistry , thermal expansion , crystal structure , thermodynamics , ion , optics , physics , organic chemistry

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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