Construction of new heteroselenometallic clusters: Formation of crownlike [Et4N]4[(μ5-WSe4)(CuI) 5(μ-I)2] and octahedral polymeric [(μ6- WSe4)Cu6I4(py)4]n from planar [Et4N]4[(μ4-WSe4)Cu ...

Qian Feng Zhang; Zhan Yu; Jihai Ding; Yinglin Song; Alexander Rothenberger; Dieter Fenske; Wa Hung Leung

doi:10.1021/ic060161p

Construction of new heteroselenometallic clusters: Formation of crownlike [Et₄N]₄[(μ₅-WSe₄)(CuI) ₅(μ-I)₂] and octahedral polymeric [(μ₆- WSe₄)Cu₆I₄(py)₄]_n from planar [Et₄N]₄[(μ₄-WSe₄)Cu ...

Qian Feng Zhang^*, Zhan Yu, Jihai Ding, Yinglin Song, Alexander Rothenberger, Dieter Fenske, Wa Hung Leung

^*Corresponding author for this work

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Abstract

Full title: Construction of new heteroselenometallic clusters: Formation of crownlike [Et₄N]₄[(μ₅-WSe₄)(CuI) ₅(μ-I)₂] and octahedral polymeric [(μ₆- WSe₄)Cu₆I₄(py)₄]_n from planar [Et₄N]₄[(μ₄-WSe₄)Cu ₄I₆] with additional faces. The coplanar cluster compound [Et₄N] ₄[(μ₄-WSe₄)Cu₄I₆] (1) was prepared from reaction of [Et₄N]₂[WSe₄] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et₄N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(μ₄-WSe₄)Cu₄(Py) ₆I₂] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe₄Cu ₄ core and the formation of a neutral polymeric cluster [(μ₃-WOSe₃)Cu₃(py)₃(μ-I)] _n (3) containing a nest-shaped OWSe₃Cu₃ core and a terminal W=O bond. The interaction of cluster 1 with excess PPh ₃ in CH₂Cl₂ gave [(μ₃-WSe ₄)Cu₃(PPh₃)₃(μ₃-I)] (4) which has a cubanelike SeWSe₃Cu₃I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et₄N] ₄[(μ₅-WSe₄)(CuI)₅(μ-I) ₂] (5) which has a crownlike core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(μ₆-WSe₄)Cu ₆I₄(Py)₄]_n (6), consisting of an octahedral WSe₄Cu₆ repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm ^-2.

Original language	English (US)
Pages (from-to)	5187-5195
Number of pages	9
Journal	Inorganic chemistry
Volume	45
Issue number	13
DOIs	https://doi.org/10.1021/ic060161p
State	Published - Jun 26 2006
Externally published	Yes

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{863b15c1dc924d86b562a1ff2d497800,

title = "Construction of new heteroselenometallic clusters: Formation of crownlike [Et4N]4[(μ5-WSe4)(CuI) 5(μ-I)2] and octahedral polymeric [(μ6- WSe4)Cu6I4(py)4]n from planar [Et4N]4[(μ4-WSe4)Cu ...",

abstract = "Full title: Construction of new heteroselenometallic clusters: Formation of crownlike [Et4N]4[(μ5-WSe4)(CuI) 5(μ-I)2] and octahedral polymeric [(μ6- WSe4)Cu6I4(py)4]n from planar [Et4N]4[(μ4-WSe4)Cu 4I6] with additional faces. The coplanar cluster compound [Et4N] 4[(μ4-WSe4)Cu4I6] (1) was prepared from reaction of [Et4N]2[WSe4] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et4N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(μ4-WSe4)Cu4(Py) 6I2] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe4Cu 4 core and the formation of a neutral polymeric cluster [(μ3-WOSe3)Cu3(py)3(μ-I)] n (3) containing a nest-shaped OWSe3Cu3 core and a terminal W=O bond. The interaction of cluster 1 with excess PPh 3 in CH2Cl2 gave [(μ3-WSe 4)Cu3(PPh3)3(μ3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N] 4[(μ5-WSe4)(CuI)5(μ-I) 2] (5) which has a crownlike core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(μ6-WSe4)Cu 6I4(Py)4]n (6), consisting of an octahedral WSe4Cu6 repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm -2.",

author = "Zhang, {Qian Feng} and Zhan Yu and Jihai Ding and Yinglin Song and Alexander Rothenberger and Dieter Fenske and Leung, {Wa Hung}",

year = "2006",

month = jun,

day = "26",

doi = "10.1021/ic060161p",

language = "English (US)",

volume = "45",

pages = "5187--5195",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

Construction of new heteroselenometallic clusters: Formation of crownlike [Et₄N]₄[(μ₅-WSe₄)(CuI) ₅(μ-I)₂] and octahedral polymeric [(μ₆- WSe₄)Cu₆I₄(py)₄]_n from planar [Et₄N]₄[(μ₄-WSe₄)Cu ... / Zhang, Qian Feng; Yu, Zhan; Ding, Jihai et al.
In: Inorganic chemistry, Vol. 45, No. 13, 26.06.2006, p. 5187-5195.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Construction of new heteroselenometallic clusters

T2 - Formation of crownlike [Et4N]4[(μ5-WSe4)(CuI) 5(μ-I)2] and octahedral polymeric [(μ6- WSe4)Cu6I4(py)4]n from planar [Et4N]4[(μ4-WSe4)Cu ...

AU - Zhang, Qian Feng

AU - Yu, Zhan

AU - Ding, Jihai

AU - Song, Yinglin

AU - Rothenberger, Alexander

AU - Fenske, Dieter

AU - Leung, Wa Hung

PY - 2006/6/26

Y1 - 2006/6/26

N2 - Full title: Construction of new heteroselenometallic clusters: Formation of crownlike [Et4N]4[(μ5-WSe4)(CuI) 5(μ-I)2] and octahedral polymeric [(μ6- WSe4)Cu6I4(py)4]n from planar [Et4N]4[(μ4-WSe4)Cu 4I6] with additional faces. The coplanar cluster compound [Et4N] 4[(μ4-WSe4)Cu4I6] (1) was prepared from reaction of [Et4N]2[WSe4] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et4N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(μ4-WSe4)Cu4(Py) 6I2] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe4Cu 4 core and the formation of a neutral polymeric cluster [(μ3-WOSe3)Cu3(py)3(μ-I)] n (3) containing a nest-shaped OWSe3Cu3 core and a terminal W=O bond. The interaction of cluster 1 with excess PPh 3 in CH2Cl2 gave [(μ3-WSe 4)Cu3(PPh3)3(μ3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N] 4[(μ5-WSe4)(CuI)5(μ-I) 2] (5) which has a crownlike core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(μ6-WSe4)Cu 6I4(Py)4]n (6), consisting of an octahedral WSe4Cu6 repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm -2.

AB - Full title: Construction of new heteroselenometallic clusters: Formation of crownlike [Et4N]4[(μ5-WSe4)(CuI) 5(μ-I)2] and octahedral polymeric [(μ6- WSe4)Cu6I4(py)4]n from planar [Et4N]4[(μ4-WSe4)Cu 4I6] with additional faces. The coplanar cluster compound [Et4N] 4[(μ4-WSe4)Cu4I6] (1) was prepared from reaction of [Et4N]2[WSe4] with 4 equiv of CuI in N,N-dimethylformamide (DMF) solution in the presence of [Et4N]I. Treatment of 1 with pyridine (py) in dry MeCN gave the neutral cluster [(μ4-WSe4)Cu4(Py) 6I2] (2) in good yield. Recrystallization of 1 from py/i-PrOH resulted in the reorganization of the coplanar WSe4Cu 4 core and the formation of a neutral polymeric cluster [(μ3-WOSe3)Cu3(py)3(μ-I)] n (3) containing a nest-shaped OWSe3Cu3 core and a terminal W=O bond. The interaction of cluster 1 with excess PPh 3 in CH2Cl2 gave [(μ3-WSe 4)Cu3(PPh3)3(μ3-I)] (4) which has a cubanelike SeWSe3Cu3I core. Treatment of 1 with 1 equiv of CuI in dimethyl sulfoxide (DMSO) yielded [Et4N] 4[(μ5-WSe4)(CuI)5(μ-I) 2] (5) which has a crownlike core structure. Treatment of 1 in DMF with 2 equiv of CuI in the presence of py resulted in the formation of a two-dimensional polymeric cluster, [(μ6-WSe4)Cu 6I4(Py)4]n (6), consisting of an octahedral WSe4Cu6 repeating unit. The solid-state structures of clusters 3, 5, and 6 have been further established by X-ray crystallography. The nonlinear optical properties of 6 have been also investigated. Cluster 6 was found to exhibit good photostability and a large optical limiting effect with the limiting threshold being ca. 0.3 J cm -2.

UR - http://www.scopus.com/inward/record.url?scp=33746509743&partnerID=8YFLogxK

U2 - 10.1021/ic060161p

DO - 10.1021/ic060161p

M3 - Article

C2 - 16780343

AN - SCOPUS:33746509743

SN - 0020-1669

VL - 45

SP - 5187

EP - 5195

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 13

ER -

Construction of new heteroselenometallic clusters: Formation of crownlike [Et₄N]₄[(μ₅-WSe₄)(CuI) ₅(μ-I)₂] and octahedral polymeric [(μ₆- WSe₄)Cu₆I₄(py)₄]_n from planar [Et₄N]₄[(μ₄-WSe₄)Cu ...

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