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Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes

Title: Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes
Authors: Gallo, Elisa; Bellucci, Luca; Carlotto, Silvia; Bottaro, Gregorio; Babetto, Luca; Giordano, Luca; Marchetti, Fabio; Samaritani, Simona; Armelao, Lidia; Labella, Luca
Contributors: Gallo, Elisa; Bellucci, Luca; Carlotto, Silvia; Bottaro, Gregorio; Babetto, Luca; Giordano, Luca; Marchetti, Fabio; Samaritani, Simona; Armelao, Lidia; Labella, Luca
Publisher Information: MDPI
Publication Year: 2024
Collection: Padua Research Archive (IRIS - Università degli Studi di Padova)
Subject Terms: 8-hydroxyquinoline N-oxide; aluminium; heterometallic complexe; lanthanide; quantum mechanical calculation; X-ray structure
Description: A reaction in anhydrous toluene between the formally unsaturated fragment [Ln(hfac)(3)] (Ln(3+) = Eu3+, Gd3+ and Er3+; Hhfac = hexafluoroacetylacetone) and [Al(qNO)(3)] (HqNO = 8-hydroxyquinoline N-oxide), here prepared for the first time from [Al((OBu)-Bu-t)(3)] and HqNO, affords the dinuclear heterometallic compounds [Ln(hfac)(3)Al(qNO)(3)] (Ln(3+) = Eu3+, Gd3+ and Er3+) 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)(3)] with [Alq(3)] (Hq = 8-hydroxyquinoline) in the same conditions yields a heterometallic product of composition [Eu(hfac)(3)Alq(3)]. A recrystallization attempt from hot heptane in air produced single crystals of two different morphologies and compositions: [Eu-2(hfac)(6)Al(2)q(4)(OH)(2)] and [Eu-2(hfac)(6)(mu -Hq)(2)]. The latter compound can be directly prepared from [Eu(hfac)(3)] and Hq at room temperature. Quantum mechanical calculations confirm (i) the higher stability of [Eu(hfac)(3)Al(qNO)(3)] vs. the corresponding [Eu(hfac)(3)Alq(3)] 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.
Document Type: article in journal/newspaper
File Description: ELETTRONICO
Language: English
Relation: info:eu-repo/semantics/altIdentifier/pmid/38257364; info:eu-repo/semantics/altIdentifier/wos/WOS:001152748400001; volume:29; issue:2; firstpage:451; numberofpages:16; journal:MOLECULES; https://hdl.handle.net/11577/3508210
DOI: 10.3390/molecules29020451
Availability: https://hdl.handle.net/11577/3508210; https://doi.org/10.3390/molecules29020451; https://www.mdpi.com/1420-3049/29/2/451
Rights: info:eu-repo/semantics/openAccess ; license:Creative commons ; license uri:http://creativecommons.org/licenses/by/4.0/
Accession Number: edsbas.8CF5E5CC
Database: BASE