期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 105, 期 48, 页码 18708-18713出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0804789105
关键词
negative linear compression; negative thermal expansion; high-pressure; framework materials; flexibility
资金
- Trinity College, Cambridge
Silver(I) hexacyanocobaltate(III), Ag-3[Co(CN)(6)], shows a large negative linear compressibility (NLC, linear expansion under hydrostatic pressure) at ambient temperature at all pressures up to our experimental limit of 7.65(2) GPa. This behavior is qualitatively unaffected by a transition at 0.19 GPa to a new phase Ag-3[Co(CN)(6)]-II, whose structure is reported here. The high-pressure phase also shows anisotropic thermal expansion with large uniaxial negative thermal expansion (NTE, expansion on cooling). In both phases, the NLC/NTE effect arises as the rapid compression/contraction of layers of silver atoms-weakly bound via argentophilic interactions-is translated via flexing of the covalent network lattice into an expansion along a perpendicular direction. It is proposed that framework materials that contract along a specific direction on heating while expanding macroscopically will, in general, also expand along the same direction under hydrostatic pressure while contracting macroscopically.
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