Novel One-Dimensional Organic–Inorganic Polyoxometalate Hybrids Constructed from Heteropolymolybdate Units and Copper–Aminoacid Complexes

Zhao, Junwei; Zhang, Jingli; Li, Yanzhou; Cao, Jing; Chen, Lijuan

doi:10.1021/cg500019g

Cited by 47 publications

(13 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…83−86 All these suggest that amino acids are useful ligands; however, reports on POMs with amino acids are underdeveloped, 87−96 although researchers have devoted great efforts to the reactions of POMs with amino acids. Lately, our group prepared two novel 1D heteropolymolybdates with copper−arg connectors [Cu(arg 97 Enlightened by the above results, we decided to explore the reactions of POMs with TM, Ln, and amino acid ligands. Nevertheless, the preparation of PTLHDs with amino acid ligands remains a rigorous challenge due to the following four main reasons: (i) it is well-known that the system containing TM, Ln, POMs, and organic components often results in immediate precipitation rather than crystallization; 31,32,36,38,42,98,99 (ii) highly negative charge PTLHDs are unfavorable to combine amino acid ligands; (iii) TM or Ln ions easily coordinate to the external O atoms of highly negative POMs in water solution, which renders combination of TM or Ln cations with amino acid ligands difficult; and (iv) the spatial hindrance of PTLHDs is unfavorable to integrating relatively large ligands.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

First Tungstoantimonate-Based Transition-Metal–Lanthanide Heterometallic Hybrids Functionalized by Amino Acid Ligands

Zhao

Cao

et al. 2014

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

By the routine aqueous solution method, a series of transitionmetal−lanthanide heterometallic tungstoantimonates [Ln(H 2 O) 8 ] 2 -[Fe 4 (H 2 O) 8 (thr) 2 ][B-β-SbW 9 O 33 ] 2 ·22H 2 O [Ln = Pr III (1), Nd III (2), Sm III (3), Eu III (4), Gd III (5), Dy III (6), Lu III (7), thr = threonine] were prepared and structurally characterized by multiple testing techniques. The common structural characteristic of 1−7 is that they are isomorphous and all consist of a [Fe 4 (H 2 O) 8 (thr) 2 (B-β-SbW 9 O 33 ) 2 ] 6− subunit with two supporting [Ln(H 2 O) 8 ] 3+ cations on both sides. It should be pointed out that two thr ligands in the [Fe 4 (H 2 O) 8 (thr) 2 (B-β-SbW 9 O 33 ) 2 ] 6− subunit substitute for two water ligands in the classical [Fe 4 (H 2 O) 10 (B-β-SbW 9 O 33 ) 2 ] 6− polyoxoanion. As far as we know, 1−7 represents the first organic−inorganic tungstoantimonate hybrids consisting of transition metal and lanthanide cations and amino acid components. The fluorescence behavior of 4 has been measured and manifests the remarkable fluorescence feature resulting from the emission signature of Eu III cations. Furthermore, the solid-state electrochemistry and electrocatalytic performances of 1 have been measured in 0.5 mol L −1 Na 2 SO 4 +H 2 SO 4 aqueous solution, and the results show that 1 illustrates comparatively apparent catalytic activities toward the BrO 3 − and H 2 O 2 reduction. The magnetic properties of 3 and 6 have been studied. ■ INTRODUCTION Polyoxometalates (POMs) represent an special family of intriguing metal−oxygen cluster compounds formed by high oxidation state early transition metals (preferably Mo, W, V, and Nb) bearing tremendous diverse structures, seductive properties, and latent applications in catalysis, magnetism, electronics, photoluminescence, pharmaceutical, and materials science. 1−9 Highly negative charge, O-enriched lacunary POMs, can act as one kind of outstanding multidentate nucleophilic candidates to coordinate to transition-metal (TM) or lanthanoid (Ln) ions to construct neoteric TM or Ln encapsulated POM aggregates with varying metal centers, alluring topological architectures and novel properties, which can also make more magnetic or catalytic components implant to the POM cluster skeletons. Therefore, the exploration and discovery of TM-or Ln-functionalized POMs have attracted considerable interest over the past few decades. Hitherto, a vast amount of TM-or Ln-substituted POMs have been sequentially discovered. 10−19 In contrast, explorations on POM-based TM−Ln heterometallic derivatives (PTLHDs) still remain less developed, although their unmatched diversities and physicochemical properties entail them to become candidates for magnetic materials or optical sensing materials. 20−22 Less work dedicated to PTLHDs mainly lies in an inescapable competing reaction between electrophilic Ln and TM cations with nucleophilic POM precursors within a system. 23 Therefore, the search and preparation of POMbased TM−Ln heterometallic materials will remain a longstanding and persisting chall...

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

First Tungstoantimonate-Based Transition-Metal–Lanthanide Heterometallic Hybrids Functionalized by Amino Acid Ligands

Zhao

Cao

et al. 2014

Crystal Growth & Design

Self Cite

View full text Add to dashboard Cite

show abstract

“…A weak antiferromagnetic Cu–Cu coupling exists according to this plot. Other complexes containing Cu 2+ also exhibit similar trends . The 1/χ M versus T plot is fitted by the Curie–Weiss law from 2.0 to 300.0 K. The Curie constant ( C ) is 1.65 emu K mol –1 , and the Weiss constant (θ) is −2.04 K. The fitting result further proves that antiferromagnetic Cu–Cu interactions occur.…”

Section: Resultsmentioning

confidence: 55%

Evans–Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic–Organic Hybrid Compounds with Copper–Organic Coordination Complexes: Synthesis and Oxidation Catalysis

Hou

Wang

et al. 2017

Inorg. Chem.

View full text Add to dashboard Cite

Four new hybrid architectures containing a [CoMoHO] polyoxoanion, (en)[Cu(ptz)(HO)][CoMoHO]·24HO (1), (Hbim)[{Cu(bim)(HO)}{CoMoHO}]·5HO (2), H[Cu(dpdo)(HO)][{Cu(dpdo)(HO)(CHCN)}{CoMoHO}]·9HO (3), and (Hbpp)[{Cu(HO)}{NaCoMoHO}]·10HO (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [CoMoHO] as the guest. Compound 2 is constructed from [CoMoHO] polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [CoMoHO] polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [CoMoHO] polyoxoanions joined together by Na and Cu cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.

show abstract

“…Recently, the application of POMs as photocatalysts have attracted widely attention. Some literature reports indicate that POMs can degradation dye of water pollution . Compounds 1 and 2 degrade methylene blue (MB) at different time under UV‐light irradiation.…”

Section: Resultsmentioning

confidence: 99%

Organic‐Inorganic Hybrid Supramolecular Assemblies Based on Isomers [H_xAs₂Mo₆O₂₆]^(6–x)– Clusters

Zhao

Cong

et al. 2017

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

The arsenomolybdates [H2As2Mo6O26(H2O)]·(H2biyb)2·2H2O (1) and [H3As2Mo6O26]·(H3pt)2 (2) [biyb = 1,4‐bis(imidazol‐1‐ylmethyl)benzene, pt = 4′‐(3′′‐pyridyl)‐2,3′:6′3′′‐terpyridine] were synthesized via hydrothermal method. The structures of the compounds were characterized by single‐crystal X‐ray diffraction analyses, elemental analyses, IR spectroscopy, and TG analysis. Compounds 1 and 2 exhibit two isomeric forms of [HxAs2Mo6O26](6–x)–. The structure of 1 is constructed from the B‐type [H2As2Mo6O26(H2O)]4– polyanions and free biyb ligands via weak interactions to form 3D supramolecular framework with a {3·4·53·6}{3·43·52}{3·5·6}2{3·52}2 topology structure. In compound 2, the A‐type [H3As2Mo6O26]3– clusters are surrounded by pt ligands through hydrogen bond interactions forming 3D supramolecular framework with a {43·63}2{46·66·83} topology structure. The electrochemical behaviors, electrocatalytic and photocatalytic activities of 1 and 2 are detected.

show abstract

Novel One-Dimensional Organic–Inorganic Polyoxometalate Hybrids Constructed from Heteropolymolybdate Units and Copper–Aminoacid Complexes

Cited by 47 publications

References 77 publications

First Tungstoantimonate-Based Transition-Metal–Lanthanide Heterometallic Hybrids Functionalized by Amino Acid Ligands

First Tungstoantimonate-Based Transition-Metal–Lanthanide Heterometallic Hybrids Functionalized by Amino Acid Ligands

Evans–Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic–Organic Hybrid Compounds with Copper–Organic Coordination Complexes: Synthesis and Oxidation Catalysis

Organic‐Inorganic Hybrid Supramolecular Assemblies Based on Isomers [H_xAs₂Mo₆O₂₆]^(6–x)– Clusters

Contact Info

Product

Resources

About

Novel One-Dimensional Organic–Inorganic Polyoxometalate Hybrids Constructed from Heteropolymolybdate Units and Copper–Aminoacid Complexes

Cited by 47 publications

References 77 publications

First Tungstoantimonate-Based Transition-Metal–Lanthanide Heterometallic Hybrids Functionalized by Amino Acid Ligands

First Tungstoantimonate-Based Transition-Metal–Lanthanide Heterometallic Hybrids Functionalized by Amino Acid Ligands

Evans–Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic–Organic Hybrid Compounds with Copper–Organic Coordination Complexes: Synthesis and Oxidation Catalysis

Organic‐Inorganic Hybrid Supramolecular Assemblies Based on Isomers [HxAs2Mo6O26](6–x)– Clusters

Contact Info

Product

Resources

About

Organic‐Inorganic Hybrid Supramolecular Assemblies Based on Isomers [H_xAs₂Mo₆O₂₆]^(6–x)– Clusters