Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies
The peroxo‐bridged di‐cerium(IV)‐di‐lithium‐containing polyoxometalate [(CeIV2O2)Li2(P2W16O59)2]16− (Ce2Li2P4W32) is synthesized in a one‐pot aqueous synthetic procedure and isolated as a hydrated mixed alkali salt, K13.6Na1.4Li[(CeIV2O2)Li2(P2W16O59)2]·32H2O (KNaLi‐Ce2Li2P4W32). The novel polyanion...
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2025-07-01
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| Online Access: | https://doi.org/10.1002/ceur.202500082 |
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| author | Anusree Sundar Danica Bajuk‐Bogdanović Gordana Ćirić‐Marjanović Talha Nisar Veit Wagner Arnulf Materny Geoffrey B. Jameson Bassem S. Bassil Ulrich Kortz |
| author_facet | Anusree Sundar Danica Bajuk‐Bogdanović Gordana Ćirić‐Marjanović Talha Nisar Veit Wagner Arnulf Materny Geoffrey B. Jameson Bassem S. Bassil Ulrich Kortz |
| author_sort | Anusree Sundar |
| collection | DOAJ |
| description | The peroxo‐bridged di‐cerium(IV)‐di‐lithium‐containing polyoxometalate [(CeIV2O2)Li2(P2W16O59)2]16− (Ce2Li2P4W32) is synthesized in a one‐pot aqueous synthetic procedure and isolated as a hydrated mixed alkali salt, K13.6Na1.4Li[(CeIV2O2)Li2(P2W16O59)2]·32H2O (KNaLi‐Ce2Li2P4W32). The novel polyanion Ce2Li2P4W32 comprises a side‐on peroxo‐group bridging two cerium(IV) and two lithium ions, which are encapsulated between two dilacunary, face‐on {P2W16} Wells–Dawson units, with a vacant site in each of the two belts. The polyanion Ce2Li2P4W32 is characterized in the solid state by single‐crystal X‐ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and Raman spectroscopy and in solution by 31P NMR and Raman spectroscopy, respectively. Ce2Li2P4W32 and the peroxo‐group are shown to be highly stable in a large pH range and up to almost boiling temperatures, but at the same time the polyanion is reactive toward oxidation of triphenylphosphine, involving the peroxo group and the cerium(IV) centers. |
| format | Article |
| id | doaj-art-6fed2cbae07b4cb0938a588b6720768f |
| institution | DOAJ |
| issn | 2751-4765 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryEurope |
| spelling | doaj-art-6fed2cbae07b4cb0938a588b6720768f2025-08-20T03:11:57ZengWiley-VCHChemistryEurope2751-47652025-07-0134n/an/a10.1002/ceur.202500082Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative StudiesAnusree Sundar0Danica Bajuk‐Bogdanović1Gordana Ćirić‐Marjanović2Talha Nisar3Veit Wagner4Arnulf Materny5Geoffrey B. Jameson6Bassem S. Bassil7Ulrich Kortz8School of Science Constructor University Campus Ring 1 28759 Bremen GermanyFaculty of Physical Chemistry University of Belgrade Studentski trg 12‐16 11158 Belgrade SerbiaFaculty of Physical Chemistry University of Belgrade Studentski trg 12‐16 11158 Belgrade SerbiaSchool of Science Constructor University Campus Ring 1 28759 Bremen GermanySchool of Science Constructor University Campus Ring 1 28759 Bremen GermanySchool of Science Constructor University Campus Ring 1 28759 Bremen GermanySchool of Food Technology and Natural Sciences Massey University Private Bag 11 222 Palmerston North 4442 New ZealandSchool of Science Constructor University Campus Ring 1 28759 Bremen GermanySchool of Science Constructor University Campus Ring 1 28759 Bremen GermanyThe peroxo‐bridged di‐cerium(IV)‐di‐lithium‐containing polyoxometalate [(CeIV2O2)Li2(P2W16O59)2]16− (Ce2Li2P4W32) is synthesized in a one‐pot aqueous synthetic procedure and isolated as a hydrated mixed alkali salt, K13.6Na1.4Li[(CeIV2O2)Li2(P2W16O59)2]·32H2O (KNaLi‐Ce2Li2P4W32). The novel polyanion Ce2Li2P4W32 comprises a side‐on peroxo‐group bridging two cerium(IV) and two lithium ions, which are encapsulated between two dilacunary, face‐on {P2W16} Wells–Dawson units, with a vacant site in each of the two belts. The polyanion Ce2Li2P4W32 is characterized in the solid state by single‐crystal X‐ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray photoelectron spectroscopy, and Raman spectroscopy and in solution by 31P NMR and Raman spectroscopy, respectively. Ce2Li2P4W32 and the peroxo‐group are shown to be highly stable in a large pH range and up to almost boiling temperatures, but at the same time the polyanion is reactive toward oxidation of triphenylphosphine, involving the peroxo group and the cerium(IV) centers.https://doi.org/10.1002/ceur.202500082ceriumoxidationRaman spectroscopyperoxo‐speciespolyoxometalates |
| spellingShingle | Anusree Sundar Danica Bajuk‐Bogdanović Gordana Ćirić‐Marjanović Talha Nisar Veit Wagner Arnulf Materny Geoffrey B. Jameson Bassem S. Bassil Ulrich Kortz Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies ChemistryEurope cerium oxidation Raman spectroscopy peroxo‐species polyoxometalates |
| title | Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies |
| title_full | Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies |
| title_fullStr | Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies |
| title_full_unstemmed | Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies |
| title_short | Highly Shielded Peroxo‐Cerium(IV)‐Containing Polyoxometalate: Synthesis, Structure, and Oxidative Studies |
| title_sort | highly shielded peroxo cerium iv containing polyoxometalate synthesis structure and oxidative studies |
| topic | cerium oxidation Raman spectroscopy peroxo‐species polyoxometalates |
| url | https://doi.org/10.1002/ceur.202500082 |
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