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Issue 25, 2009
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Lanthanide complexes in hybrid halometallate materials: interconversion between a novel 2D microporous framework and a 1D zigzag chain structure of iodoargentates templated by octakis-solvated terbium(III) cation

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Abstract

Octakis solvated terbium iodide complexes [Tb(DMSO)8]I3 (1) and [Tb(DMF)8]I3 (2) (DMSO = dimethylsulfoxide; DMF = dimethylformamide) were used as synthons to construct novel iodoargentate fabrics. Reaction of 1 with 6 equivalents of AgI in the presence of NH4I produced a novel framework compound [Tb(DMSO)8]2[Ag2(μ-I)3I2][Ag53-I)4(μ-I)4]2∞ (3) involving alternate layers of discrete [Tb(DMSO)8]3+ cation, [Ag2I5]3− anion and a 2D microporous sheet of the composition [Ag5I8]3−, whereas similar reaction of 2 yielded [Tb(DMF)8][Ag64-I)23-I)2(μ-I)5]1∞ (4) with a 1D zigzag structure. The two structural forms are completely inter-convertible on mutual exchange of DMSO and DMF ligands, the partial substitution of the former ligand in 3 yielding a mixed-ligand complex [Tb(DMF)6.7(DMSO)1.3][Ag64-I)23-I)2(μ-I)5]1∞ (5). Single crystal X-ray structures are reported for all the complexes. Thermo-gravimetric analyses of these complexes show that thermal stability decreases in the order 4 > 2 > 3 > 1, whereas the diffuse reflectance spectra of 3 and 4 exhibit an optical band gap of about 3.7 eV, thus revealing the insulator nature of these hybrid iodoargentates. Compared to solvated terbium iodide complexes 1 and 2, the high energy transitions in the excitation spectra of the iodoargentate complexes 3 and 4 are quenched by a process which can best be attributed to the auto-ionization of the carriers in the above materials.

Graphical abstract: Lanthanide complexes in hybrid halometallate materials: interconversion between a novel 2D microporous framework and a 1D zigzag chain structure of iodoargentates templated by octakis-solvated terbium(III) cation

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Publication details

The article was received on 19 Feb 2009, accepted on 17 Apr 2009 and first published on 18 May 2009


Article type: Paper
DOI: 10.1039/B903576A
Citation: Dalton Trans., 2009,0, 4954-4961
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    Lanthanide complexes in hybrid halometallate materials: interconversion between a novel 2D microporous framework and a 1D zigzag chain structure of iodoargentates templated by octakis-solvated terbium(III) cation

    S. Mishra, E. Jeanneau, G. Ledoux and S. Daniele, Dalton Trans., 2009, 0, 4954
    DOI: 10.1039/B903576A

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