A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure
The Ga-rich gallides of the alkali metals present an interesting, yet still scarcely investigated case of polyanionic cluster compounds with subtle variations in the character of their chemical bonding. In the present work, the Ga richest phases K<inline-formula><math display="inline&q...
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MDPI AG
2020-11-01
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| Series: | Crystals |
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| Online Access: | https://www.mdpi.com/2073-4352/10/11/1052 |
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| author | Martha Falk Marco Wendorff Caroline Röhr |
| author_facet | Martha Falk Marco Wendorff Caroline Röhr |
| author_sort | Martha Falk |
| collection | DOAJ |
| description | The Ga-rich gallides of the alkali metals present an interesting, yet still scarcely investigated case of polyanionic cluster compounds with subtle variations in the character of their chemical bonding. In the present work, the Ga richest phases K<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>13</mn></msub></semantics></math></inline-formula>, RbGa<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>7</mn></msub></semantics></math></inline-formula>, and CsGa<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>7</mn></msub></semantics></math></inline-formula>, which are formally electron-precise <i>Zintl</i>/<i>Wade</i> cluster compounds, are systematically studied with respect to a partial substitution of Ga by In and Hg. The pure hepta-gallides <i>A</i>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>7</mn></msub></semantics></math></inline-formula> (<i>A</i> = Rb/Cs; <inline-formula><math display="inline"><semantics><mrow><mi>R</mi><mover accent="true"><mn>3</mn><mo>¯</mo></mover><mi>m</mi></mrow></semantics></math></inline-formula>), which were formerly obtained from Ga-rich melts in powder form only, were crystallized from Hg-rich melts. Herein, up to 9.9/13.6% (Rb/Cs) of Ga could be substituted by In, which partly takes the four-bonded [<i>M</i><inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>] dumbbells connecting layers of Ga-icosahedra. Even though the structures are electron precise, the pseudo band gap does not coincide with the Fermi level. In the most Ga-rich potassium compound K<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>13</mn></msub></semantics></math></inline-formula> (<inline-formula><math display="inline"><semantics><mrow><mi>C</mi><mi>m</mi><mi>c</mi><mi>m</mi></mrow></semantics></math></inline-formula>) only 1.2% of In and 2.7% of Hg could be incorporated. Although Rb<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>13</mn></msub></semantics></math></inline-formula> remains unknown, ternary variants containing 5.2 to 8.2% In could be obtained; this structure is also stabilized by a small Hg-proportion. The likewise closed-shell 3D polyanion consists of all-<i>exo</i>-bonded Ga-icosahedra and <i>closo</i> [Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>11</mn></msub></semantics></math></inline-formula>] clusters, which are connected by two tetrahedrally four-bonded Ga<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mo>−</mo></msup></semantics></math></inline-formula> and a trigonal-planar three-bonded Ga<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mn>0</mn></msup></semantics></math></inline-formula>. The aspects of the electronic structures and the site-specific Ga↦Hg/In substitution in the polyanion (“coloring”) are discussed for the title compounds and other mixed Ga/In trielides. |
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| institution | Directory Open Access Journal |
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| language | English |
| last_indexed | 2024-03-10T14:44:08Z |
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| spelling | doaj.art-afc8d092beda436095209ebbc678dab82023-11-20T21:31:34ZengMDPI AGCrystals2073-43522020-11-011011105210.3390/cryst10111052A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type StructureMartha Falk0Marco Wendorff1Caroline Röhr2Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, D-79104 Freiburg, GermanyInstitut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, D-79104 Freiburg, GermanyInstitut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, D-79104 Freiburg, GermanyThe Ga-rich gallides of the alkali metals present an interesting, yet still scarcely investigated case of polyanionic cluster compounds with subtle variations in the character of their chemical bonding. In the present work, the Ga richest phases K<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>13</mn></msub></semantics></math></inline-formula>, RbGa<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>7</mn></msub></semantics></math></inline-formula>, and CsGa<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>7</mn></msub></semantics></math></inline-formula>, which are formally electron-precise <i>Zintl</i>/<i>Wade</i> cluster compounds, are systematically studied with respect to a partial substitution of Ga by In and Hg. The pure hepta-gallides <i>A</i>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>7</mn></msub></semantics></math></inline-formula> (<i>A</i> = Rb/Cs; <inline-formula><math display="inline"><semantics><mrow><mi>R</mi><mover accent="true"><mn>3</mn><mo>¯</mo></mover><mi>m</mi></mrow></semantics></math></inline-formula>), which were formerly obtained from Ga-rich melts in powder form only, were crystallized from Hg-rich melts. Herein, up to 9.9/13.6% (Rb/Cs) of Ga could be substituted by In, which partly takes the four-bonded [<i>M</i><inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>2</mn></msub></semantics></math></inline-formula>] dumbbells connecting layers of Ga-icosahedra. Even though the structures are electron precise, the pseudo band gap does not coincide with the Fermi level. In the most Ga-rich potassium compound K<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>13</mn></msub></semantics></math></inline-formula> (<inline-formula><math display="inline"><semantics><mrow><mi>C</mi><mi>m</mi><mi>c</mi><mi>m</mi></mrow></semantics></math></inline-formula>) only 1.2% of In and 2.7% of Hg could be incorporated. Although Rb<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>3</mn></msub></semantics></math></inline-formula>Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>13</mn></msub></semantics></math></inline-formula> remains unknown, ternary variants containing 5.2 to 8.2% In could be obtained; this structure is also stabilized by a small Hg-proportion. The likewise closed-shell 3D polyanion consists of all-<i>exo</i>-bonded Ga-icosahedra and <i>closo</i> [Ga<inline-formula><math display="inline"><semantics><msub><mrow></mrow><mn>11</mn></msub></semantics></math></inline-formula>] clusters, which are connected by two tetrahedrally four-bonded Ga<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mo>−</mo></msup></semantics></math></inline-formula> and a trigonal-planar three-bonded Ga<inline-formula><math display="inline"><semantics><msup><mrow></mrow><mn>0</mn></msup></semantics></math></inline-formula>. The aspects of the electronic structures and the site-specific Ga↦Hg/In substitution in the polyanion (“coloring”) are discussed for the title compounds and other mixed Ga/In trielides.https://www.mdpi.com/2073-4352/10/11/1052gallidesindiummercuryalkali metalscluster compoundscrystal growth |
| spellingShingle | Martha Falk Marco Wendorff Caroline Röhr A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure Crystals gallides indium mercury alkali metals cluster compounds crystal growth |
| title | A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure |
| title_full | A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure |
| title_fullStr | A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure |
| title_full_unstemmed | A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure |
| title_short | A Coloring Study of the Ga Richest Alkali Gallides: New In- and Hg-Containing Gallides with the RbGa<sub>7</sub>- and the K<sub>3</sub>Ga<sub>13</sub>-Type Structure |
| title_sort | coloring study of the ga richest alkali gallides new in and hg containing gallides with the rbga sub 7 sub and the k sub 3 sub ga sub 13 sub type structure |
| topic | gallides indium mercury alkali metals cluster compounds crystal growth |
| url | https://www.mdpi.com/2073-4352/10/11/1052 |
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