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

Jinfang Zhang; Suci Meng; Yinglin Song; Junyi Yang; Hongyang Wei; Wenjiang Huang; Marie P. Cifuentes; Mark G. Humphrey; Chi Zhang

doi:10.1039/c0nj00674b

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

Jinfang Zhang, Suci Meng, Yinglin Song, Junyi Yang, Hongyang Wei, Wenjiang Huang, Marie P. Cifuentes, Mark G. Humphrey, Chi Zhang

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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][W₆S₂₄Ag ₆]}_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.

Original language	English
Pages (from-to)	328-338
Number of pages	11
Journal	New Journal of Chemistry
Volume	35
Issue number	2
DOIs	https://doi.org/10.1039/c0nj00674b
Publication status	Published - Feb 2011

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

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][W6S24Ag 6]}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.",

author = "Jinfang Zhang and Suci Meng and Yinglin Song and Junyi Yang and Hongyang Wei and Wenjiang Huang and Cifuentes, {Marie P.} and Humphrey, {Mark G.} and Chi Zhang",

year = "2011",

month = feb,

doi = "10.1039/c0nj00674b",

language = "English",

volume = "35",

pages = "328--338",

journal = "New Journal of Chemistry",

issn = "1144-0546",

publisher = "Royal Society of Chemistry",

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T1 - Syntheses and NLO properties of 1D heterothiometallic anionic W/S/Ag clusters possessing solvento-ytterbium cation-directed isomeric skeletons

AU - Zhang, Jinfang

AU - Meng, Suci

AU - Song, Yinglin

AU - Yang, Junyi

AU - Wei, Hongyang

AU - Huang, Wenjiang

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

AU - Zhang, Chi

PY - 2011/2

Y1 - 2011/2

N2 - 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][W6S24Ag 6]}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.

AB - 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][W6S24Ag 6]}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.

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DO - 10.1039/c0nj00674b

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JF - New Journal of Chemistry

IS - 2

ER -

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

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