Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates
New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster...
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| Format: | Article |
| Language: | English |
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MDPI AG
2016-05-01
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| Series: | Inorganics |
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| Online Access: | http://www.mdpi.com/2304-6740/4/2/14 |
| _version_ | 1811225980159655936 |
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| author | Nerea Andino Beñat Artetxe Santiago Reinoso Pablo Vitoria Leire San Felices Jose I. Martínez Fernando López Arbeloa Juan M. Gutiérrez-Zorrilla |
| author_facet | Nerea Andino Beñat Artetxe Santiago Reinoso Pablo Vitoria Leire San Felices Jose I. Martínez Fernando López Arbeloa Juan M. Gutiérrez-Zorrilla |
| author_sort | Nerea Andino |
| collection | DOAJ |
| description | New organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H(POC11H9)2(α-HBW11O39)] (TBA-1) and [N(C4H9)4]3[H(POC11H9)2(α-SiW11O39)] (TBA-2). Liquid-solution UV–Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of 1H-, 13C- and 31P-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)2(α-HBW11O39)]3− (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates. |
| first_indexed | 2024-04-12T09:17:36Z |
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| id | doaj.art-d0d543627e01499cb162e456f298370a |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-04-12T09:17:36Z |
| publishDate | 2016-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-d0d543627e01499cb162e456f298370a2022-12-22T03:38:48ZengMDPI AGInorganics2304-67402016-05-01421410.3390/inorganics4020014inorganics4020014Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type PolyoxotungstatesNerea Andino0Beñat Artetxe1Santiago Reinoso2Pablo Vitoria3Leire San Felices4Jose I. Martínez5Fernando López Arbeloa6Juan M. Gutiérrez-Zorrilla7Departamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainServicios Generales de Investigación SGIker, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainDepartamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainBCMaterials, Parque Científico y Tecnológico de Bizkaia, Derio 48160, SpainDepartamento de Química Inorgánica, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, Bilbao 48080, SpainNew organophosphonate derivatives of monovacant Keggin-type polyoxotungstates that contain naphthyl groups have been synthesized and characterized in both solid state and solution. Single-crystal structural analysis shows that two phosphonate groups occupy the vacant position of the lacunary cluster unit in the isostructural compounds [N(C4H9)4]3[H(POC11H9)2(α-HBW11O39)] (TBA-1) and [N(C4H9)4]3[H(POC11H9)2(α-SiW11O39)] (TBA-2). Liquid-solution UV–Vis transmittance and solid-state diffuse reflectance spectroscopy studies reveal the presence of a new absorption band in the visible region, the charge transfer character of which has been further confirmed by time-dependent density functional theory (TD-DFT) calculations. The latter evidence that the charge transfer process is dominated by transitions from the highest occupied molecular orbital (HOMO), localized in the aromatic ring of the organic group, to the lowest unoccupied molecular orbital (LUMO), localized in the Keggin anion. Photoluminescence studies show that the fluorescent properties of the 1-naphthylmethylphosphonate group are quenched upon its incorporation into the inorganic oxo-tungstate skeleton. The solution stability of the hybrid clusters has been evaluated by a combination of 1H-, 13C- and 31P-Nuclear Magnetic Resonance spectroscopy and Electrospray Ionization-Mass Spectrometry. The hybrid polyanion [H(POC11H9)2(α-HBW11O39)]3− (1) herein constitutes the first structurally characterized organo-p-block containing borotungstate, and hence it confirms that this strategy for the organic functionalization of polyoxometalate clusters can be applied to new platforms belonging to the family of group-13 heteropolyoxotungstates.http://www.mdpi.com/2304-6740/4/2/14polyoxometalatesorganophosphonatescharge transferfluorescencesolution stability |
| spellingShingle | Nerea Andino Beñat Artetxe Santiago Reinoso Pablo Vitoria Leire San Felices Jose I. Martínez Fernando López Arbeloa Juan M. Gutiérrez-Zorrilla Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates Inorganics polyoxometalates organophosphonates charge transfer fluorescence solution stability |
| title | Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates |
| title_full | Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates |
| title_fullStr | Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates |
| title_full_unstemmed | Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates |
| title_short | Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates |
| title_sort | naphthyl containing organophosphonate derivatives of keggin type polyoxotungstates |
| topic | polyoxometalates organophosphonates charge transfer fluorescence solution stability |
| url | http://www.mdpi.com/2304-6740/4/2/14 |
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