Alkali Metal Directed Assembly of Heterometallic Vv/M (M = Na, K, Cs) Coordination Polymers: Structures, Topological Analysis, and Oxidation Catalytic Properties.
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| Title: | Alkali Metal Directed Assembly of Heterometallic Vv/M (M = Na, K, Cs) Coordination Polymers: Structures, Topological Analysis, and Oxidation Catalytic Properties. |
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| Authors: | Gupta, Samik1, Kirillova, Marina V.1, Guedes da Silva, M. Fátima C.1,2 fatima.guedes@ist.utl.pt, Pombeiro, Armando J. L.1 pombeiro@ist.utl.pt, Kirillov, Alexander M.1 kirillov@ist.utl.pt |
| Source: | Inorganic Chemistry. 8/5/2013, Vol. 52 Issue 15, p8601-8611. 11p. |
| Subjects: | Alkali metal compounds, Molecular self-assembly, Coordination polymers, Chemical structure, Oxidation, Nuclear magnetic resonance spectroscopy, Cyclohexanones |
| Abstract: | The reactions of [VO(acac)2] with bis(salicylaldehyde)-oxaloyldihydrazone (H4L) and an alkali metal carbonate M2CO3 (M = K, Na, Cs), in EtOH/H2O medium upon reflux, resulted in the generation of three new heterometallic VV/M materials, namely the 1D [(VO2)2(µ4-L){Na2(µ-H2O)2(H2O)2}]n (1), 2D [{V(µ-O)2}2(µ4-L){K2(µ-H2O)2(H2O)2}]n (2), and 3D [{V(µ-O)(µ3-O)}2(µ8-L){Cs2(µ-H2O)2(H2O)2}]n (3) coordination polymers. They were isolated as air-stable solids and fully characterized by IR, UV-vis, 1H, and 51V NMR spectroscopy, ESI-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses, the latter showing that 1-3 are constructed from the resembling [(VO2)2(µ4/8-L)]2- blocks assembled by the differently bound aqua-metal [M2(µ-H2O)2(H2O)2]2+ moieties (M = Na, K, Cs). The main distinctive features of 1-3 arise from the different coordination numbers of Na (5), K (7), and Cs (9) atoms, thus increasing the complexity of the resulting networks from the ladder-like 1D chains in 1 to double 2D layers in 2, and layer-pillared 3D framework in 3. The topological analysis of 2 disclosed a uninodal 4-connected underlying net with a rare kgm [Shubnikov plane net (3.6.3.6)/kagome pattern] topology, while 3 features a trinodal 4,7,8-connected underlying net with an unprecedented topology. Compounds 1-3 also show solubility in water (S25 °C ≈ 4-7 mg mL-1) and were applied as efficient precatalysts for the homogeneous oxidation of cyclohexane by aqueous H2O2, under mild conditions (50 °C) in MeCN/H2O medium and in the presence of an acid promoter. Total yields (based on substrate) of cyclohexanol and cyclohexanone up to 36% and turnover numbers (TONs) up to 5700 were achieved. [ABSTRACT FROM AUTHOR] |
| Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
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| Items | – Name: Title Label: Title Group: Ti Data: Alkali Metal Directed Assembly of Heterometallic V<superscript>v</superscript>/M (M = Na, K, Cs) Coordination Polymers: Structures, Topological Analysis, and Oxidation Catalytic Properties. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Gupta%2C+Samik%22">Gupta, Samik</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Kirillova%2C+Marina+V%2E%22">Kirillova, Marina V.</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Guedes+da+Silva%2C+M%2E+Fátima+C%2E%22">Guedes da Silva, M. Fátima C.</searchLink><relatesTo>1,2</relatesTo><i> fatima.guedes@ist.utl.pt</i><br /><searchLink fieldCode="AR" term="%22Pombeiro%2C+Armando+J%2E+L%2E%22">Pombeiro, Armando J. L.</searchLink><relatesTo>1</relatesTo><i> pombeiro@ist.utl.pt</i><br /><searchLink fieldCode="AR" term="%22Kirillov%2C+Alexander+M%2E%22">Kirillov, Alexander M.</searchLink><relatesTo>1</relatesTo><i> kirillov@ist.utl.pt</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Inorganic+Chemistry%22">Inorganic Chemistry</searchLink>. 8/5/2013, Vol. 52 Issue 15, p8601-8611. 11p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Alkali+metal+compounds%22">Alkali metal compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+self-assembly%22">Molecular self-assembly</searchLink><br /><searchLink fieldCode="DE" term="%22Coordination+polymers%22">Coordination polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+structure%22">Chemical structure</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation%22">Oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Nuclear+magnetic+resonance+spectroscopy%22">Nuclear magnetic resonance spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Cyclohexanones%22">Cyclohexanones</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: The reactions of [VO(acac)2] with bis(salicylaldehyde)-oxaloyldihydrazone (H4L) and an alkali metal carbonate M2CO3 (M = K, Na, Cs), in EtOH/H2O medium upon reflux, resulted in the generation of three new heterometallic VV/M materials, namely the 1D [(VO2)2(µ4-L){Na2(µ-H2O)2(H2O)2}]n (1), 2D [{V(µ-O)2}2(µ4-L){K2(µ-H2O)2(H2O)2}]n (2), and 3D [{V(µ-O)(µ3-O)}2(µ8-L){Cs2(µ-H2O)2(H2O)2}]n (3) coordination polymers. They were isolated as air-stable solids and fully characterized by IR, UV-vis, 1H, and 51V NMR spectroscopy, ESI-MS(±), elemental, thermal, and single-crystal X-ray diffraction analyses, the latter showing that 1-3 are constructed from the resembling [(VO2)2(µ4/8-L)]2- blocks assembled by the differently bound aqua-metal [M2(µ-H2O)2(H2O)2]2+ moieties (M = Na, K, Cs). The main distinctive features of 1-3 arise from the different coordination numbers of Na (5), K (7), and Cs (9) atoms, thus increasing the complexity of the resulting networks from the ladder-like 1D chains in 1 to double 2D layers in 2, and layer-pillared 3D framework in 3. The topological analysis of 2 disclosed a uninodal 4-connected underlying net with a rare kgm [Shubnikov plane net (3.6.3.6)/kagome pattern] topology, while 3 features a trinodal 4,7,8-connected underlying net with an unprecedented topology. Compounds 1-3 also show solubility in water (S25 °C ≈ 4-7 mg mL-1) and were applied as efficient precatalysts for the homogeneous oxidation of cyclohexane by aqueous H2O2, under mild conditions (50 °C) in MeCN/H2O medium and in the presence of an acid promoter. Total yields (based on substrate) of cyclohexanol and cyclohexanone up to 36% and turnover numbers (TONs) up to 5700 were achieved. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Inorganic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/ic400743h Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 11 StartPage: 8601 Subjects: – SubjectFull: Alkali metal compounds Type: general – SubjectFull: Molecular self-assembly Type: general – SubjectFull: Coordination polymers Type: general – SubjectFull: Chemical structure Type: general – SubjectFull: Oxidation Type: general – SubjectFull: Nuclear magnetic resonance spectroscopy Type: general – SubjectFull: Cyclohexanones Type: general Titles: – TitleFull: Alkali Metal Directed Assembly of Heterometallic Vv/M (M = Na, K, Cs) Coordination Polymers: Structures, Topological Analysis, and Oxidation Catalytic Properties. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Gupta, Samik – PersonEntity: Name: NameFull: Kirillova, Marina V. – PersonEntity: Name: NameFull: Guedes da Silva, M. Fátima C. – PersonEntity: Name: NameFull: Pombeiro, Armando J. L. – PersonEntity: Name: NameFull: Kirillov, Alexander M. IsPartOfRelationships: – BibEntity: Dates: – D: 05 M: 08 Text: 8/5/2013 Type: published Y: 2013 Identifiers: – Type: issn-print Value: 00201669 Numbering: – Type: volume Value: 52 – Type: issue Value: 15 Titles: – TitleFull: Inorganic Chemistry Type: main |
| ResultId | 1 |
