Novel three-dimensional organic-inorganic heterometallic hybrid built by sandwich-type tetra-mn-substituted germanotungstates through mixed 3d and 4f metal linkers

Hai Yan Zhao; Jun Wei Zhao; Bai Feng Yang; Huan He; Guo Yu Yang

doi:10.1021/cg4014575

Novel three-dimensional organic-inorganic heterometallic hybrid built by sandwich-type tetra-mn-substituted germanotungstates through mixed 3d and 4f metal linkers

Hai Yan Zhao
, Jun Wei Zhao^*
, Bai Feng Yang
, Huan He
, Guo Yu Yang

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Beijing Institute of Technology
Henan University
CAS - Fujian Institute of Research on the Structure of Matter

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

42 Citations (Scopus)

Abstract

The reaction of trivacant Keegin germanotungstate [A-α-GeW ₉O₃₄]^10- with Mn²⁺ and Ce ⁴⁺ cations in the presence of oxalate ligand under hydrothermal conditions led to the isolation of a novel organic-inorganic hybrid 3d-4f heterometallic germanotungstate K₄Na₄[Ce ₂(ox)₃(H₂O)₂]₂{[Mn(H ₂O)₃]₂[Mn₄(GeW₉O ₃₄)₂(H₂O)₂]·14H₂O (1) (ox = oxalate), which has been characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and single-crystal X-ray crystallography. Interestingly, each tetra-Mn^II-substituted sandwich-type unit acts as 14-dentate ligands to link eight Ce³⁺ centers and six Mn²⁺ centers further into a three-dimensional (3D) architecture. The 3D structure can be considered as two parts: one is the two-dimensional layer formed by sandwich-type [Mn₄(H ₂O)₂(GeW₉O₃₄)₂] ^12- fragments and Mn²⁺ linkers; the other layer is constructed from Ce³⁺ cations and oxalate bridges, and the two layers are combined together alternately through W-O-Ce-O-W linkers, resulting in the 3D framework. Notably, 1 exhibits the first 3d-4f 3D organic-inorganic hybrid framework constructed by sandwich-type TM-substituted polyoxoanions and mixed 3d and 4f metal linkers in POM chemistry.

Original language	English
Pages (from-to)	5169-5174
Number of pages	6
Journal	Crystal Growth and Design
Volume	13
Issue number	12
DOIs	https://doi.org/10.1021/cg4014575
Publication status	Published - 4 Dec 2013

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title = "Novel three-dimensional organic-inorganic heterometallic hybrid built by sandwich-type tetra-mn-substituted germanotungstates through mixed 3d and 4f metal linkers",

abstract = "The reaction of trivacant Keegin germanotungstate [A-α-GeW 9O34]10- with Mn2+ and Ce 4+ cations in the presence of oxalate ligand under hydrothermal conditions led to the isolation of a novel organic-inorganic hybrid 3d-4f heterometallic germanotungstate K4Na4[Ce 2(ox)3(H2O)2]2\{[Mn(H 2O)3]2[Mn4(GeW9O 34)2(H2O)2]·14H2O (1) (ox = oxalate), which has been characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and single-crystal X-ray crystallography. Interestingly, each tetra-MnII-substituted sandwich-type unit acts as 14-dentate ligands to link eight Ce3+ centers and six Mn2+ centers further into a three-dimensional (3D) architecture. The 3D structure can be considered as two parts: one is the two-dimensional layer formed by sandwich-type [Mn4(H 2O)2(GeW9O34)2] 12- fragments and Mn2+ linkers; the other layer is constructed from Ce3+ cations and oxalate bridges, and the two layers are combined together alternately through W-O-Ce-O-W linkers, resulting in the 3D framework. Notably, 1 exhibits the first 3d-4f 3D organic-inorganic hybrid framework constructed by sandwich-type TM-substituted polyoxoanions and mixed 3d and 4f metal linkers in POM chemistry.",

author = "Zhao, \{Hai Yan\} and Zhao, \{Jun Wei\} and Yang, \{Bai Feng\} and Huan He and Yang, \{Guo Yu\}",

year = "2013",

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doi = "10.1021/cg4014575",

language = "English",

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AU - Zhao, Hai Yan

AU - Zhao, Jun Wei

AU - Yang, Bai Feng

AU - He, Huan

AU - Yang, Guo Yu

PY - 2013/12/4

Y1 - 2013/12/4

N2 - The reaction of trivacant Keegin germanotungstate [A-α-GeW 9O34]10- with Mn2+ and Ce 4+ cations in the presence of oxalate ligand under hydrothermal conditions led to the isolation of a novel organic-inorganic hybrid 3d-4f heterometallic germanotungstate K4Na4[Ce 2(ox)3(H2O)2]2{[Mn(H 2O)3]2[Mn4(GeW9O 34)2(H2O)2]·14H2O (1) (ox = oxalate), which has been characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and single-crystal X-ray crystallography. Interestingly, each tetra-MnII-substituted sandwich-type unit acts as 14-dentate ligands to link eight Ce3+ centers and six Mn2+ centers further into a three-dimensional (3D) architecture. The 3D structure can be considered as two parts: one is the two-dimensional layer formed by sandwich-type [Mn4(H 2O)2(GeW9O34)2] 12- fragments and Mn2+ linkers; the other layer is constructed from Ce3+ cations and oxalate bridges, and the two layers are combined together alternately through W-O-Ce-O-W linkers, resulting in the 3D framework. Notably, 1 exhibits the first 3d-4f 3D organic-inorganic hybrid framework constructed by sandwich-type TM-substituted polyoxoanions and mixed 3d and 4f metal linkers in POM chemistry.

AB - The reaction of trivacant Keegin germanotungstate [A-α-GeW 9O34]10- with Mn2+ and Ce 4+ cations in the presence of oxalate ligand under hydrothermal conditions led to the isolation of a novel organic-inorganic hybrid 3d-4f heterometallic germanotungstate K4Na4[Ce 2(ox)3(H2O)2]2{[Mn(H 2O)3]2[Mn4(GeW9O 34)2(H2O)2]·14H2O (1) (ox = oxalate), which has been characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and single-crystal X-ray crystallography. Interestingly, each tetra-MnII-substituted sandwich-type unit acts as 14-dentate ligands to link eight Ce3+ centers and six Mn2+ centers further into a three-dimensional (3D) architecture. The 3D structure can be considered as two parts: one is the two-dimensional layer formed by sandwich-type [Mn4(H 2O)2(GeW9O34)2] 12- fragments and Mn2+ linkers; the other layer is constructed from Ce3+ cations and oxalate bridges, and the two layers are combined together alternately through W-O-Ce-O-W linkers, resulting in the 3D framework. Notably, 1 exhibits the first 3d-4f 3D organic-inorganic hybrid framework constructed by sandwich-type TM-substituted polyoxoanions and mixed 3d and 4f metal linkers in POM chemistry.

UR - https://www.scopus.com/pages/publications/84889828709

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SN - 1528-7483

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JO - Crystal Growth and Design

JF - Crystal Growth and Design

IS - 12

ER -

Novel three-dimensional organic-inorganic heterometallic hybrid built by sandwich-type tetra-mn-substituted germanotungstates through mixed 3d and 4f metal linkers

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