Ag1+xTlO2 (0.03 ≤ x ≤ 0.18), Novel Adaptations of the Delafossite Structure Type Featuring Subvalent Silver1. Issue 6 (25th February 2014)

• Record Type: Journal Article
• Authors: Nuss, Jürgen; Dietrich, Volker; Curda, Jan; Jansen, Martin
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 640:Issue 6(2014)
• Page Start: 1063
• Page End: 1068
• Publication Date: 2014-02-25
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201400050
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A family of novel variations of the delafossite type of structure, Ag<sub>1+<italic>x</italic></sub>TlO<sub>2</sub>, was synthesized and characterized. For three members the crystal structures were solved and refined on single crystal data: Ag<sub>1+</sub><sub><italic>α</italic></sub>TlO<sub>2</sub> [<italic>α</italic> = 0.18, <italic>P</italic><tex-math notation="tex"><![CDATA[$\bar{3}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2sx68mr" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><italic>m</italic>1, <italic>Z</italic> = 1, <italic>a</italic> = 3.40427(9), <italic>c</italic> = 6.1296(1) Å, <italic>R</italic><sub>1</sub> = 0.033, 126 independent reflections]; Ag<sub>1+</sub><sub><italic>β</italic></sub>TlO<sub>2</sub> [<italic>β</italic> = 0.09, <italic>R</italic><tex-math notation="tex"><![CDATA[$\bar{3}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2sx68jq" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><italic>m</italic>, <italic>Z</italic> = 6, <italic>a</italic> = 3.40685(8), <italic>c</italic> = 37.5953(9) Å, <italic>R</italic><sub>1</sub> = 0.039, 214 independent reflections]; Ag<sub>1+</sub><sub><italic>γ</italic></sub>TlO<sub>2</sub> [<italic>γ</italic> = 0.03, <italic>R</italic><tex-math notation="tex"><![CDATA[$\bar{3}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh2sx68k7" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><italic>m</italic>, <italic>Z</italic> = 9, <italic>a</italic> = 3.403(2), <italic>c</italic> = 56.67(3) Å, <italic>R</italic><sub>1</sub> = 0.038, 397 independent reflections]. Different from the conventional delafossite structure, part of the silver layers accommodate an excess of ca. 0.18 silver atoms per layer, thus generating a subvalent bonding state of silver. In accordance with the structural findings, the new silver oxthallates(III) are metallic conductors, and show reduced binding energies for the silver 3<italic>d</italic><sub>5/2</sub> states, compared to silver(I) oxide.</p> </abstract>