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Issue 44, 2008
From the journal:

Dalton Transactions

Reactions of metal iodides as a simple route to heterometallics: synthesis, structural transformations, thermal and luminescent properties of novel hybrid iodoargentate derivatives templated by [YL8]3+ or [YL7]3+cations (L = DMF or DMSO)†

Shashank Mishra,*a   Erwann Jeanneau,b   Stéphane Daniele*a  and  Gilles Ledouxc  

* Corresponding authors

a Université Lyon 1, IRCELYON, 2 Avenue A. Einstein, Villeurbanne, France
E-mail: mishrashashank74@rediffmail.com
Fax: +33 472445399
Tel: +33 472445329

b Université Lyon 1, Centre de Diffractométrie, Villeurbanne, France

c Université Lyon 1, Laboratoire de Physico Chimie des Matériaux Luminescent, CNRS UMR 5620, 10 rue A. M. Ampère, Villeurbanne, France

Abstract

A 1 : 3 molar reaction of YI3 and AgI in dimethylformamide (DMF) in the presence of NH4I afforded [Y(DMF)8][Ag3(μ3-I)(μ-I)3I2] (1) with good yield, whereas the similar reaction in dimethylsulfoxide (DMSO) gave complexes [Y(DMSO)8][Ag2(μ-I)3I2] (2) and/or [Y(DMSO)8]2[Ag4(μ3-I)2(μ-I)4I2][I]2 (3), depending on the reaction and crystallization conditions. These discrete heterometallic hybrid compounds 1–3 undergo solid- and solution-state transformations via condensation of iodoargentate anions. So in the confined and solvent-free environment of paratone, crystals of 1 transformed into a 1D zig-zag structure [Y(DMF)8]3+[Ag6(μ4-I)2(μ3-I)2(μ-I)5]1∞3− (4), whereas those of 2 were first converted into 3 and finally into [Y(DMSO)7]4[Ag4(μ3-I)4I4]3 (5). In solution phase, re-crystalization of 1 or 2 from DMSO–toluene gave 3 as an exclusive species, whereas reaction of 1 with 3 equiv of AgI in DMF afforded 4 with good yield. Alternatively, 4 could also be synthesized with excellent yield from a 1 : 6 molar reaction of YI3 and AgI. The above transformations suggest that, for a given metal–organic cation, an iodometallate cluster with higher nuclearity is thermodynamically more stable. Single crystal X-ray structures are reported for all the compounds and a mechanism for the structural transformation of 2 to 3 is proposed. In addition, spectroscopic, thermo-gravimetric and luminescent properties of the complexes 1, 3 and 4, which were obtained exclusively and in pure form, are also described.

Graphical abstract: Reactions of metal iodides as a simple route to heterometallics: synthesis, structural transformations, thermal and luminescent properties of novel hybrid iodoargentate derivatives templated by [YL8]3+ or [YL7]3+ cations (L = DMF or DMSO)

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Article information

DOI
https://doi.org/10.1039/B809964B
Article type
Paper
Submitted
12 Jun 2008
Accepted
04 Aug 2008
First published
06 Oct 2008

Dalton Trans., 2008, 6296-6304

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Reactions of metal iodides as a simple route to heterometallics: synthesis, structural transformations, thermal and luminescent properties of novel hybrid iodoargentate derivatives templated by [YL8]3+ or [YL7]3+ cations (L = DMF or DMSO)

S. Mishra, E. Jeanneau, S. Daniele and G. Ledoux, Dalton Trans., 2008, 6296 DOI: 10.1039/B809964B

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