Issue 6, 2010

Syntheses and crystal structures of four new silver(i) iodates with d0-transition metal cations

Abstract

Systematic explorations of new phases in the AgI-TiIV/VV/MoVI-iodate systems led to four new quaternary silver iodates, namely, Ag2Ti(IO3)6, Ag2(VO2)(IO3)3, Ag2(V2O4)(IO3)4, and Ag2(MoO2)(IO3)4. They represent the first examples of silver iodates containing d0 transition metal cations. Ag2Ti(IO3)6 is isostructural with K2Ti(IO3)6 and its structure features a zero-dimensional (0D) [Ti(IO3)6]2− anionic unit composed of non-distorted TiO6 octahedron corner-sharing with six IO3 groups. Such anions are further bridged by Ag+ ions into a 3D network. In both Ag2(VO2)(IO3)3 and Ag2(V2O4)(IO3)4, each vanadium(V) is octahedrally coordinated by one terminal and two bridging oxo anions as well as three iodate anions in unidentate fashion. Neighboring VO6 octahedra form a 1D vanadium(V) oxide chain via corner-sharing oxo anions, such chains are further decorated by iodate anions in bridging or unidentate fashion. Ag2(VO2)(IO3)3 features a thick triple layer composed of two Ag(2)(VO2)(IO3)2 and one Ag(1)IO3 sheet whereas Ag2(V2O4)(IO3)4 features a 3D network composed of 1D [(V2O4)(IO3)3] anionic chains along the c-axis that are interconnected by [Ag4(IO3)2]2+ clusters. Ag2(MoO2)(IO3)4 is isostructural with K2(MoO2)(IO3)4 and its structure features a 3D network built from 0D [(MoO2)(IO3)4]2− anions further interconnected by Ag+ ions. Optical and luminescent property measurements as well as band structure calculations based on density functional theory (DFT) methods have also been performed.

Graphical abstract: Syntheses and crystal structures of four new silver(i) iodates with d0-transition metal cations

Supplementary files

Article information

Article type
Paper
Submitted
01 Sep 2009
Accepted
26 Oct 2009
First published
03 Dec 2009

Dalton Trans., 2010,39, 1473-1479

Syntheses and crystal structures of four new silver(I) iodates with d0-transition metal cations

C. Sun, C. Hu, F. Kong, B. Yang and J. Mao, Dalton Trans., 2010, 39, 1473 DOI: 10.1039/B917907K

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