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Issue 2, 2011
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Syntheses and NLO properties of 1D heterothiometallic anionic W/S/Ag clusters possessing solvento-ytterbium cation-directed isomeric skeletons

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Abstract

The sequential addition to [WS4]2 of different solvent-coordinated ytterbium cations as templates and silver iodide as Ag+ source afforded the heterothiometallic clusters {[Yb(DMSO)7][Yb(DMSO)8][W6S24Ag6]}n1 (DMSO = dimethyl sulfoxide), {[Yb(DMF)8][W3S12Ag3]}n2 (DMF = N,N′-dimethylformamide) and {[Yb(HMP)4(NO3)2][WS4Ag]}n3 (HMP = hexamethylphosphoramide) with isomeric anionic skeletons and in high yields. 1–3 have been fully characterized by elemental analysis, IR and UV-vis spectroscopies, and single-crystal X-ray crystallographic studies. 1 possesses a 1D anionic helical chain with unusual hexavalent repeat units, a structure directed by the combination of seven- and eight-coordinated ytterbium cations, 2 exhibits an unusual 1D anionic zigzag chain, while 3 contains a 1D anionic linear chain. Z-scan studies (532 nm, 8 ns pulses) reveal that 1 and 2 possess strong third-order nonlinear optical properties. Density functional theory and time-dependent density functional theory calculations at the B3LYP/LanL2DZf+6-31G* level were performed on 1–3 to rationalize their experimental absorption spectra.

Graphical abstract: Syntheses and NLO properties of 1D heterothiometallic anionic W/S/Ag clusters possessing solvento-ytterbium cation-directed isomeric skeletons

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Publication details

The article was received on 31 Aug 2010, accepted on 17 Oct 2010 and first published on 15 Nov 2010


Article type: Paper
DOI: 10.1039/C0NJ00674B
New J. Chem., 2011,35, 328-338

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    Syntheses and NLO properties of 1D heterothiometallic anionic W/S/Ag clusters possessing solvento-ytterbium cation-directed isomeric skeletons

    J. Zhang, S. Meng, Y. Song, J. Yang, H. Wei, W. Huang, M. P. Cifuentes, M. G. Humphrey and C. Zhang, New J. Chem., 2011, 35, 328
    DOI: 10.1039/C0NJ00674B

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