Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order
Mixed-metal cyanides (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN adopt an AuCN-type structure in which metal-cyanide chains pack on a hexagonal lattice with metal atoms arranged in sheets. The interactions between and within the metal-cyanide chains are investigated using density functio...
| Main Authors: | , , , , , , , |
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| Format: | Journal article |
| Language: | English |
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American Chemical Society
2020
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| author | Hibble, SJ Chippindale, AM Zbiri, M Rees, NH Keeble, DS Heribert, W d’Ambrumenil, S Seifert, D |
| author_facet | Hibble, SJ Chippindale, AM Zbiri, M Rees, NH Keeble, DS Heribert, W d’Ambrumenil, S Seifert, D |
| author_sort | Hibble, SJ |
| collection | OXFORD |
| description | Mixed-metal cyanides (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN adopt an AuCN-type structure in which metal-cyanide chains pack on a hexagonal lattice with metal atoms arranged in sheets. The interactions between and within the metal-cyanide chains are investigated using density functional theory (DFT) calculations, 13C solid-state NMR (SSNMR), and X-ray pair distribution function (PDF) measurements. Long-range metal and cyanide order is found within the chains: (−Cu–NC–Au–CN−)∞, (−Ag–NC–Au–CN−)∞, and (−Cu–NC–Ag–NC–Au–CN−)∞. Although Bragg diffraction studies establish that there is no long-range order between chains, X-ray PDF results show that there is local order between chains. In (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN, there is a preference for unlike metal atoms occurring as nearest neighbors within the metal sheets. A general mathematical proof shows that the maximum average number of heterometallic nearest-neighbor interactions on a hexagonal lattice with two types of metal atoms is four. Calculated energies of periodic structural models show that those with four unlike nearest neighbors are most favorable. Of these, models in space group Immm give the best fits to the X-ray PDF data out to 8 Å, providing good descriptions of the short- and medium-range structures. This result shows that interactions beyond those of nearest neighbors must be considered when determining the structures of these materials. Such interactions are also important in (Cu1/3Ag1/3Au1/3)CN, leading to the adoption of a structure in Pmm2 containing mixed Cu–Au and Ag-only sheets arranged to maximize the numbers of Cu···Au nearest- and next-nearest-neighbor interactions. |
| first_indexed | 2024-03-06T18:47:47Z |
| format | Journal article |
| id | oxford-uuid:0f1dec63-088e-4a9f-b3f6-57c8b19f0cb8 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-06T18:47:47Z |
| publishDate | 2020 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:0f1dec63-088e-4a9f-b3f6-57c8b19f0cb82022-03-26T09:49:36ZIntra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional orderJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:0f1dec63-088e-4a9f-b3f6-57c8b19f0cb8MetalsLayersGoldInorganic carbon compounds,Chemical structureEnglishSymplectic ElementsAmerican Chemical Society2020Hibble, SJChippindale, AMZbiri, MRees, NHKeeble, DSHeribert, Wd’Ambrumenil, SSeifert, DMixed-metal cyanides (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN adopt an AuCN-type structure in which metal-cyanide chains pack on a hexagonal lattice with metal atoms arranged in sheets. The interactions between and within the metal-cyanide chains are investigated using density functional theory (DFT) calculations, 13C solid-state NMR (SSNMR), and X-ray pair distribution function (PDF) measurements. Long-range metal and cyanide order is found within the chains: (−Cu–NC–Au–CN−)∞, (−Ag–NC–Au–CN−)∞, and (−Cu–NC–Ag–NC–Au–CN−)∞. Although Bragg diffraction studies establish that there is no long-range order between chains, X-ray PDF results show that there is local order between chains. In (Cu1/2Au1/2)CN and (Ag1/2Au1/2)CN, there is a preference for unlike metal atoms occurring as nearest neighbors within the metal sheets. A general mathematical proof shows that the maximum average number of heterometallic nearest-neighbor interactions on a hexagonal lattice with two types of metal atoms is four. Calculated energies of periodic structural models show that those with four unlike nearest neighbors are most favorable. Of these, models in space group Immm give the best fits to the X-ray PDF data out to 8 Å, providing good descriptions of the short- and medium-range structures. This result shows that interactions beyond those of nearest neighbors must be considered when determining the structures of these materials. Such interactions are also important in (Cu1/3Ag1/3Au1/3)CN, leading to the adoption of a structure in Pmm2 containing mixed Cu–Au and Ag-only sheets arranged to maximize the numbers of Cu···Au nearest- and next-nearest-neighbor interactions. |
| spellingShingle | Metals Layers Gold Inorganic carbon compounds, Chemical structure Hibble, SJ Chippindale, AM Zbiri, M Rees, NH Keeble, DS Heribert, W d’Ambrumenil, S Seifert, D Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order |
| title | Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order |
| title_full | Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order |
| title_fullStr | Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order |
| title_full_unstemmed | Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order |
| title_short | Intra- and interchain interactions in (Cu1/2Au1/2)CN, (Ag1/2Au1/2)CN, and (Cu1/3Ag1/3Au1/3)CN and their effect on one-, two-, and three-dimensional order |
| title_sort | intra and interchain interactions in cu1 2au1 2 cn ag1 2au1 2 cn and cu1 3ag1 3au1 3 cn and their effect on one two and three dimensional order |
| topic | Metals Layers Gold Inorganic carbon compounds, Chemical structure |
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