Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

Xin Zhao; Feng Zhou; Quan Liu; Qiu Fang Chen; Jun Yi Yang; Wen Hua Zhang; Ying Lin Song; Jian Ping Lang

doi:10.1021/acs.inorgchem.5b02765

Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

Xin Zhao
, Feng Zhou
, Quan Liu
, Qiu Fang Chen
, Jun Yi Yang
, Wen Hua Zhang^*
, Ying Lin Song
, Jian Ping Lang

^*Corresponding author for this work

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

31 Scopus citations

Abstract

In the absence/presence of S₈, the one-pot assembly of [Et₄N][TpWS₃] [1; Tp∗ = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)₄]PF₆ and bis-or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N′,N′-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp WS₃Cu₂Cl)₂(dppe)] (2), [Tp WS₃Cu₄(dppp)₂(μ₄-Cl)(μ-Cl)]PF₆·MeCN (3·MeCN), [(Tp WS₃Cu₃)₂(μ₄-Cl)(μ-Cl)₂(dpppS₂)] (4), [(Tp WS₃Cu₂Cl)₂(dppbS₂)]·2MeCN·2H₂O (5·2MeCN·2H₂O), [(Tp WS₃Cu₃Cl₂)₂(dppbS₂)] (6), and [(Tp WS₃Cu₃)₂(Ph₂PS₂)₃(μ₆-Cl)_0.5](PF₆)_0.5·0.75CH₂Cl₂ (7·0.75CH₂Cl₂). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, ¹H and ³¹P{¹H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp WS₃Cu₂] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS₂ ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S₈. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S₈, leads to an unexpected ligand degradation to give the [Ph₂PS₂]^"' anions. Three [Ph₂PS₂]^"' anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ₆-Cl^-. The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability Î3; values in the range of 4.71 × 10^-30-1.02 × 10^-29 esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.

Original language	English
Pages (from-to)	1861-1871
Number of pages	11
Journal	Inorganic Chemistry
Volume	55
Issue number	4
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02765
State	Published - 15 Feb 2016
Externally published	Yes

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10.1021/acs.inorgchem.5b02765

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@article{363db2805b3c412fad38aefede3d3536,

title = "Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines",

abstract = "In the absence/presence of S8, the one-pot assembly of [Et4N][TpWS3] [1; Tp∗ = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis-or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N′,N′-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp WS3Cu2Cl)2(dppe)] (2), [Tp WS3Cu4(dppp)2(μ4-Cl)(μ-Cl)]PF6·MeCN (3·MeCN), [(Tp WS3Cu3)2(μ4-Cl)(μ-Cl)2(dpppS2)] (4), [(Tp WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp WS3Cu3)2(Ph2PS2)3(μ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, 1H and 31P\{1H\} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2]{"}' anions. Three [Ph2PS2]{"}' anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ6-Cl-. The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability {\^I}3; values in the range of 4.71 × 10-30-1.02 × 10-29 esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.",

author = "Xin Zhao and Feng Zhou and Quan Liu and Chen, \{Qiu Fang\} and Yang, \{Jun Yi\} and Zhang, \{Wen Hua\} and Song, \{Ying Lin\} and Lang, \{Jian Ping\}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = feb,

day = "15",

doi = "10.1021/acs.inorgchem.5b02765",

language = "英语",

volume = "55",

pages = "1861--1871",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "4",

}

TY - JOUR

T1 - Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

AU - Zhao, Xin

AU - Zhou, Feng

AU - Liu, Quan

AU - Chen, Qiu Fang

AU - Yang, Jun Yi

AU - Zhang, Wen Hua

AU - Song, Ying Lin

AU - Lang, Jian Ping

PY - 2016/2/15

Y1 - 2016/2/15

N2 - In the absence/presence of S8, the one-pot assembly of [Et4N][TpWS3] [1; Tp∗ = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis-or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N′,N′-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp WS3Cu2Cl)2(dppe)] (2), [Tp WS3Cu4(dppp)2(μ4-Cl)(μ-Cl)]PF6·MeCN (3·MeCN), [(Tp WS3Cu3)2(μ4-Cl)(μ-Cl)2(dpppS2)] (4), [(Tp WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp WS3Cu3)2(Ph2PS2)3(μ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, 1H and 31P{1H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2]"' anions. Three [Ph2PS2]"' anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ6-Cl-. The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability Î3; values in the range of 4.71 × 10-30-1.02 × 10-29 esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.

AB - In the absence/presence of S8, the one-pot assembly of [Et4N][TpWS3] [1; Tp∗ = hydridotris(3,5-dimethylpyrazol-1-yl)borate] with [Cu(MeCN)4]PF6 and bis-or tetraphosphine ligands 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppb), and N,N,N′,N′-tetrakis(diphenylphosphinomethyl)ethylenediamine (dppeda) produces six W-Cu-S clusters, namely, [(Tp WS3Cu2Cl)2(dppe)] (2), [Tp WS3Cu4(dppp)2(μ4-Cl)(μ-Cl)]PF6·MeCN (3·MeCN), [(Tp WS3Cu3)2(μ4-Cl)(μ-Cl)2(dpppS2)] (4), [(Tp WS3Cu2Cl)2(dppbS2)]·2MeCN·2H2O (5·2MeCN·2H2O), [(Tp WS3Cu3Cl2)2(dppbS2)] (6), and [(Tp WS3Cu3)2(Ph2PS2)3(μ6-Cl)0.5](PF6)0.5·0.75CH2Cl2 (7·0.75CH2Cl2). Compounds 2-7 are characterized by elemental analysis, IR, UV-vis, 1H and 31P{1H} NMR, electrospray ionization mass spectrometry, and X-ray crystallography. For 2, the dppe ligand bridges a pair of butterfly-shaped [Tp WS3Cu2] cores to form a double-butterfly-shaped structure. For 4, the dppp ligand is susceptible toward S association and forms an in situ generated dpppS2 ligand, supporting an octanuclear double-half-open-cubane structure and contrasting an analogous system wherein a pentanuclear motorcycle-shaped cationic cluster 3 is formed with the absence of S8. A longer dppb ligand readily converts to S-based ligands in 5 and 6, subsequently serving as bridges between a pair of a butterfly-shaped (5) and nest-shaped (6) clusters. Further use of a tetraphosphine ligand, dppeda, in the cluster formation, with the presence of S8, leads to an unexpected ligand degradation to give the [Ph2PS2]"' anions. Three [Ph2PS2]"' anions juxtapose a pair of nest-shaped cluster cores to yield an octanuclear cluster, 7, featuring a cage to encapsulate μ6-Cl-. The third-order nonlinear-optical (NLO) properties of 2-7 in N,N-dimethylformamide, investigated using a Z-scan technique at 532 nm, show that 2-6 have a reverse saturable absorption, while 7 has a notable saturable absorption. All of 2-7 exhibit a self-focusing effect with hyperpolarizability Î3; values in the range of 4.71 × 10-30-1.02 × 10-29 esu, which are 440-1000 times higher than that of 1. The formation of 4-7 from 1 through the in situ thiolation of phosphine ligands presents a new approach to the design and assembly of the W-Cu-S clusters with interesting structural arrays and better NLO properties.

UR - https://www.scopus.com/pages/publications/84958825038

U2 - 10.1021/acs.inorgchem.5b02765

DO - 10.1021/acs.inorgchem.5b02765

M3 - 文章

AN - SCOPUS:84958825038

SN - 0020-1669

VL - 55

SP - 1861

EP - 1871

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 4

ER -

Diverse Tp-Capped W-Cu-S Clusters from One-Pot Assembly Involving in Situ Thiolation of Phosphines

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