Low‐Temperature Topochemical Transformation of Bi13Pt3I7 into the New Layered Honeycomb Metal Bi12Pt3I5. Issue 51 (28th October 2014)

• Record Type: Journal Article
• Authors: Kaiser, Martin; Rasche, Bertold; Isaeva, Anna; Ruck, Michael
• Is Part Of: Chemistry. Volume 20:Issue 51(2014)
• Page Start: 17152
• Page End: 17160
• Publication Date: 2014-10-28
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201404789
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Ordered single‐crystals of the metallic subiodide Bi<sub>13</sub>Pt<sub>3</sub>I<sub>7</sub> were grown and treated with <italic>n</italic>‐butyllithium. At 45 °C, complete pseudomorphosis to Bi<sub>12</sub>Pt<sub>3</sub>I<sub>5</sub> was achieved within two days. The new compound is air‐stable and contains the same <inline-formula><alternatives><tex-math notation="tex"><![CDATA[${{{\hfill 2\atop \hfill \infty }}}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2qsv59jk" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></alternatives></inline-formula>[(PtBi<sub>8/2</sub>)<sub>3</sub>I]<sup><italic>n</italic>+</sup> honeycomb nets and iodide layers as the starting material Bi<sub>13</sub>Pt<sub>3</sub>I<sub>7</sub>, but does not include <inline-formula><alternatives><tex-math notation="tex"><![CDATA[${{{\hfill 1\atop \hfill \infty }}}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2qsv59k4" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></alternatives></inline-formula>[BiI<sub>2</sub>I<sub>4/2</sub>]<sup>−</sup> iodidobismuthate strands. Electron microscopy and X‐ray diffraction studies of solid intermediates visualize the process of the topochemical crystal‐to‐crystal transformation. In the electronic band structures of Bi<sub>13</sub>Pt<sub>3</sub>I<sub>7</sub> and Bi<sub>12</sub>Pt<sub>3</sub>I<sub>5</sub>, the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi<sub>13</sub>Pt<sub>3</sub>I<sub>7</sub> into Bi<sub>12</sub>Pt<sub>3</sub>I<sub>5</sub>, the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi<sub>13</sub>Pt<sub>3</sub>I<sub>7</sub> the intermetallic layers do not interact across the iodidobismuthate spacers (two‐dimensional metal), they couple in Bi<sub>12</sub>Pt<sub>3</sub>I<sub>5</sub> and form a three‐dimensional metal.</p> </abstract>