Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks

Xiao Zhang; Zhihui Yi; Liyan Zhao; Qian Chen; Xianmo Gu; Jiqing Xu; Xaolin Wang; Chao Yang; Xianzhu Xu; Wujiong Xia

doi:10.1039/b906313g

Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks

Xiao Zhang, Zhihui Yi, Liyan Zhao, Qian Chen, Xianmo Gu, Jiqing Xu, Xaolin Wang, Chao Yang, Xianzhu Xu, Wujiong Xia^*

^*Corresponding author for this work

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

21 Citations (Scopus)

Abstract

Three supramolecular architectures based on α-Keggin-type polyoxometalates have been synthesized hydrothermally, and their structures have been characterized by elemental analyses, infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction structure analyses. [Ni(enMe)₂(H₂O)₂] ₂[Ni(enMe)₂PW^VI₉W^V ₃O₄₀]·H₂O (1) (enMe = 1,2′-propanediamine) exhibits a novel 2-D supramolecular sinusoidal layer through the interactions between transition metal complexes and 1-D covalent chains which are constructed from α-Keggin units bridged by transition metal complexes. [Ni(enMe)₂]₄{[Ni(enMe) ₂][Ni(enMe)₂(H₂O)AsW^VI ₆W^V₄V^IV₄O ₄₂]₂}·6H₂O (2), representing a 3-D supramolecular framework with 1-D channels, contains the first example of a tungstate dimer with inorganic-organic composite surfaces built up from [Ni(enMe)₂]²⁺ cation bridges and bi-capped α-Keggin polyoxometalate building blocks supporting the transition metal complex. [Ni(enMe)₂]₄{[Ni(enMe)₂][Ni(enMe) ₂(H₂O)AsMo^VI₄Mo^V ₄V^IV₈O₄₄]₂} ·8H₂O (3), showing a 3-D supramolecular framework with 1-D channels, contains the first example of a molybdoarsenate dimer formed by [Ni(enMe)₂]²⁺ cations bridging two neighboring tetra-capped α-Keggin-based molybdates that support the transition metal complex [Ni(enMe)₂H₂O]. The topological networks of the supramolecular frameworks of 2 and 3 are analogous. Crystal structural analysis reveals that the dimensionality and the organization of polyoxometalate building units in the solid state can be tuned by the steric hindrances of the polyanions. Both 2 and 3 exhibit intensive photoluminescence.

Original language	English
Pages (from-to)	9198-9206
Number of pages	9
Journal	Dalton Transactions
Issue number	42
DOIs	https://doi.org/10.1039/b906313g
Publication status	Published - 2009
Externally published	Yes

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@article{0087e14780654405847ea1c694d6b55e,

title = "Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks",

abstract = "Three supramolecular architectures based on α-Keggin-type polyoxometalates have been synthesized hydrothermally, and their structures have been characterized by elemental analyses, infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction structure analyses. [Ni(enMe)2(H2O)2] 2[Ni(enMe)2PWVI9WV 3O40]·H2O (1) (enMe = 1,2′-propanediamine) exhibits a novel 2-D supramolecular sinusoidal layer through the interactions between transition metal complexes and 1-D covalent chains which are constructed from α-Keggin units bridged by transition metal complexes. [Ni(enMe)2]4{[Ni(enMe) 2][Ni(enMe)2(H2O)AsWVI 6WV4VIV4O 42]2}·6H2O (2), representing a 3-D supramolecular framework with 1-D channels, contains the first example of a tungstate dimer with inorganic-organic composite surfaces built up from [Ni(enMe)2]2+ cation bridges and bi-capped α-Keggin polyoxometalate building blocks supporting the transition metal complex. [Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe) 2(H2O)AsMoVI4MoV 4VIV8O44]2} ·8H2O (3), showing a 3-D supramolecular framework with 1-D channels, contains the first example of a molybdoarsenate dimer formed by [Ni(enMe)2]2+ cations bridging two neighboring tetra-capped α-Keggin-based molybdates that support the transition metal complex [Ni(enMe)2H2O]. The topological networks of the supramolecular frameworks of 2 and 3 are analogous. Crystal structural analysis reveals that the dimensionality and the organization of polyoxometalate building units in the solid state can be tuned by the steric hindrances of the polyanions. Both 2 and 3 exhibit intensive photoluminescence.",

author = "Xiao Zhang and Zhihui Yi and Liyan Zhao and Qian Chen and Xianmo Gu and Jiqing Xu and Xaolin Wang and Chao Yang and Xianzhu Xu and Wujiong Xia",

year = "2009",

doi = "10.1039/b906313g",

language = "English",

pages = "9198--9206",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "42",

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TY - JOUR

T1 - Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks

AU - Zhang, Xiao

AU - Yi, Zhihui

AU - Zhao, Liyan

AU - Chen, Qian

AU - Gu, Xianmo

AU - Xu, Jiqing

AU - Wang, Xaolin

AU - Yang, Chao

AU - Xu, Xianzhu

AU - Xia, Wujiong

PY - 2009

Y1 - 2009

N2 - Three supramolecular architectures based on α-Keggin-type polyoxometalates have been synthesized hydrothermally, and their structures have been characterized by elemental analyses, infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction structure analyses. [Ni(enMe)2(H2O)2] 2[Ni(enMe)2PWVI9WV 3O40]·H2O (1) (enMe = 1,2′-propanediamine) exhibits a novel 2-D supramolecular sinusoidal layer through the interactions between transition metal complexes and 1-D covalent chains which are constructed from α-Keggin units bridged by transition metal complexes. [Ni(enMe)2]4{[Ni(enMe) 2][Ni(enMe)2(H2O)AsWVI 6WV4VIV4O 42]2}·6H2O (2), representing a 3-D supramolecular framework with 1-D channels, contains the first example of a tungstate dimer with inorganic-organic composite surfaces built up from [Ni(enMe)2]2+ cation bridges and bi-capped α-Keggin polyoxometalate building blocks supporting the transition metal complex. [Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe) 2(H2O)AsMoVI4MoV 4VIV8O44]2} ·8H2O (3), showing a 3-D supramolecular framework with 1-D channels, contains the first example of a molybdoarsenate dimer formed by [Ni(enMe)2]2+ cations bridging two neighboring tetra-capped α-Keggin-based molybdates that support the transition metal complex [Ni(enMe)2H2O]. The topological networks of the supramolecular frameworks of 2 and 3 are analogous. Crystal structural analysis reveals that the dimensionality and the organization of polyoxometalate building units in the solid state can be tuned by the steric hindrances of the polyanions. Both 2 and 3 exhibit intensive photoluminescence.

AB - Three supramolecular architectures based on α-Keggin-type polyoxometalates have been synthesized hydrothermally, and their structures have been characterized by elemental analyses, infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and single crystal X-ray diffraction structure analyses. [Ni(enMe)2(H2O)2] 2[Ni(enMe)2PWVI9WV 3O40]·H2O (1) (enMe = 1,2′-propanediamine) exhibits a novel 2-D supramolecular sinusoidal layer through the interactions between transition metal complexes and 1-D covalent chains which are constructed from α-Keggin units bridged by transition metal complexes. [Ni(enMe)2]4{[Ni(enMe) 2][Ni(enMe)2(H2O)AsWVI 6WV4VIV4O 42]2}·6H2O (2), representing a 3-D supramolecular framework with 1-D channels, contains the first example of a tungstate dimer with inorganic-organic composite surfaces built up from [Ni(enMe)2]2+ cation bridges and bi-capped α-Keggin polyoxometalate building blocks supporting the transition metal complex. [Ni(enMe)2]4{[Ni(enMe)2][Ni(enMe) 2(H2O)AsMoVI4MoV 4VIV8O44]2} ·8H2O (3), showing a 3-D supramolecular framework with 1-D channels, contains the first example of a molybdoarsenate dimer formed by [Ni(enMe)2]2+ cations bridging two neighboring tetra-capped α-Keggin-based molybdates that support the transition metal complex [Ni(enMe)2H2O]. The topological networks of the supramolecular frameworks of 2 and 3 are analogous. Crystal structural analysis reveals that the dimensionality and the organization of polyoxometalate building units in the solid state can be tuned by the steric hindrances of the polyanions. Both 2 and 3 exhibit intensive photoluminescence.

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U2 - 10.1039/b906313g

DO - 10.1039/b906313g

M3 - Article

AN - SCOPUS:70350335031

SN - 1477-9226

SP - 9198

EP - 9206

JO - Dalton Transactions

JF - Dalton Transactions

IS - 42

ER -

Steric hindrance-dependent rational design and synthesis of three new Keggin-based supramolecular networks

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