Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes
A reaction in anhydrous toluene between the formally unsaturated fragment [Ln(hfac)<sub>3</sub>] (Ln<sup>3+</sup> = Eu<sup>3+</sup>, Gd<sup>3+</sup> and Er<sup>3+</sup>; Hhfac = hexafluoroacetylacetone) and [Al(qNO)<sub>3</sub>]...
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| Format: | Article |
| Language: | English |
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MDPI AG
2024-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/29/2/451 |
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| author | Elisa Gallo Luca Bellucci Silvia Carlotto Gregorio Bottaro Luca Babetto Luca Giordano Fabio Marchetti Simona Samaritani Lidia Armelao Luca Labella |
| author_facet | Elisa Gallo Luca Bellucci Silvia Carlotto Gregorio Bottaro Luca Babetto Luca Giordano Fabio Marchetti Simona Samaritani Lidia Armelao Luca Labella |
| author_sort | Elisa Gallo |
| collection | DOAJ |
| description | A reaction in anhydrous toluene between the formally unsaturated fragment [Ln(hfac)<sub>3</sub>] (Ln<sup>3+</sup> = Eu<sup>3+</sup>, Gd<sup>3+</sup> and Er<sup>3+</sup>; Hhfac = hexafluoroacetylacetone) and [Al(qNO)<sub>3</sub>] (HqNO = 8-hydroxyquinoline <i>N</i>-oxide), here prepared for the first time from [Al(O<sup>t</sup>Bu)<sub>3</sub>] and HqNO, affords the dinuclear heterometallic compounds [Ln(hfac)<sub>3</sub>Al(qNO)<sub>3</sub>] (Ln<sup>3+</sup> = Eu<sup>3+</sup>, Gd<sup>3+</sup> and Er<sup>3+</sup>) in high yields. The molecular structures of these new compounds revealed a dinuclear species with three phenolic oxygen atoms bridging the two metal atoms. While the europium and gadolinium complexes show the coordination number (CN) 9 for the lanthanide centre, in the complex featuring the smaller erbium ion, only two oxygens bridge the two metal atoms for a resulting CN of 8. The reaction of [Eu(hfac)<sub>3</sub>] with [Alq<sub>3</sub>] (Hq = 8-hydroxyquinoline) in the same conditions yields a heterometallic product of composition [Eu(hfac)<sub>3</sub>Alq<sub>3</sub>]. A recrystallization attempt from hot heptane in air produced single crystals of two different morphologies and compositions: [Eu<sub>2</sub>(hfac)<sub>6</sub>Al<sub>2</sub>q<sub>4</sub>(OH)<sub>2</sub>] and [Eu<sub>2</sub>(hfac)<sub>6</sub>(µ-Hq)<sub>2</sub>]. The latter compound can be directly prepared from [Eu(hfac)<sub>3</sub>] and Hq at room temperature. Quantum mechanical calculations confirm (i) the higher stability of [Eu(hfac)<sub>3</sub>Al(qNO)<sub>3</sub>] vs. the corresponding [Eu(hfac)<sub>3</sub>Alq<sub>3</sub>] and (ii) the preference of the Er complexes for the CN 8, justifying the different behaviour in terms of the Lewis acidity of the metal centre. |
| first_indexed | 2024-03-08T09:49:45Z |
| format | Article |
| id | doaj.art-76fa644634924e41928c963049029d69 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-08T09:49:45Z |
| publishDate | 2024-01-01 |
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| series | Molecules |
| spelling | doaj.art-76fa644634924e41928c963049029d692024-01-29T14:08:44ZengMDPI AGMolecules1420-30492024-01-0129245110.3390/molecules29020451Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide ComplexesElisa Gallo0Luca Bellucci1Silvia Carlotto2Gregorio Bottaro3Luca Babetto4Luca Giordano5Fabio Marchetti6Simona Samaritani7Lidia Armelao8Luca Labella9Dipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, ItalyDipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, ItalyICMATE-CNR and INSTM, Presso Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, I-35131 Padova, ItalyICMATE-CNR and INSTM, Presso Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, I-35131 Padova, ItalyDipartimento di Scienze Chimiche and INSTM, Università di Padova, via Marzolo 1, I-35131 Padova, ItalyDipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, ItalyDipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, ItalyDipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, ItalyDipartimento di Scienze Chimiche and INSTM, Università di Padova, via Marzolo 1, I-35131 Padova, ItalyDipartimento di Chimica e Chimica Industriale and CIRCC, Università di Pisa, via Giuseppe Moruzzi 13, I-56124 Pisa, ItalyA reaction in anhydrous toluene between the formally unsaturated fragment [Ln(hfac)<sub>3</sub>] (Ln<sup>3+</sup> = Eu<sup>3+</sup>, Gd<sup>3+</sup> and Er<sup>3+</sup>; Hhfac = hexafluoroacetylacetone) and [Al(qNO)<sub>3</sub>] (HqNO = 8-hydroxyquinoline <i>N</i>-oxide), here prepared for the first time from [Al(O<sup>t</sup>Bu)<sub>3</sub>] and HqNO, affords the dinuclear heterometallic compounds [Ln(hfac)<sub>3</sub>Al(qNO)<sub>3</sub>] (Ln<sup>3+</sup> = Eu<sup>3+</sup>, Gd<sup>3+</sup> and Er<sup>3+</sup>) in high yields. The molecular structures of these new compounds revealed a dinuclear species with three phenolic oxygen atoms bridging the two metal atoms. While the europium and gadolinium complexes show the coordination number (CN) 9 for the lanthanide centre, in the complex featuring the smaller erbium ion, only two oxygens bridge the two metal atoms for a resulting CN of 8. The reaction of [Eu(hfac)<sub>3</sub>] with [Alq<sub>3</sub>] (Hq = 8-hydroxyquinoline) in the same conditions yields a heterometallic product of composition [Eu(hfac)<sub>3</sub>Alq<sub>3</sub>]. A recrystallization attempt from hot heptane in air produced single crystals of two different morphologies and compositions: [Eu<sub>2</sub>(hfac)<sub>6</sub>Al<sub>2</sub>q<sub>4</sub>(OH)<sub>2</sub>] and [Eu<sub>2</sub>(hfac)<sub>6</sub>(µ-Hq)<sub>2</sub>]. The latter compound can be directly prepared from [Eu(hfac)<sub>3</sub>] and Hq at room temperature. Quantum mechanical calculations confirm (i) the higher stability of [Eu(hfac)<sub>3</sub>Al(qNO)<sub>3</sub>] vs. the corresponding [Eu(hfac)<sub>3</sub>Alq<sub>3</sub>] and (ii) the preference of the Er complexes for the CN 8, justifying the different behaviour in terms of the Lewis acidity of the metal centre.https://www.mdpi.com/1420-3049/29/2/451heterometallic complexeslanthanidesaluminium8-hydroxyquinoline <i>N</i>-oxideX-ray structurequantum mechanical calculations |
| spellingShingle | Elisa Gallo Luca Bellucci Silvia Carlotto Gregorio Bottaro Luca Babetto Luca Giordano Fabio Marchetti Simona Samaritani Lidia Armelao Luca Labella Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes Molecules heterometallic complexes lanthanides aluminium 8-hydroxyquinoline <i>N</i>-oxide X-ray structure quantum mechanical calculations |
| title | Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes |
| title_full | Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes |
| title_fullStr | Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes |
| title_full_unstemmed | Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes |
| title_short | Aluminium 8-Hydroxyquinolinate <i>N</i>-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes |
| title_sort | aluminium 8 hydroxyquinolinate i n i oxide as a precursor to heterometallic aluminium lanthanide complexes |
| topic | heterometallic complexes lanthanides aluminium 8-hydroxyquinoline <i>N</i>-oxide X-ray structure quantum mechanical calculations |
| url | https://www.mdpi.com/1420-3049/29/2/451 |
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