| Title: |
Size Selectivity in Heterolanthanide Molecular Complexes with a Ditopic Ligand |
| Authors: |
Bellucci, Luca; Fioravanti, Lorenzo; Armelao, Lidia; Bottaro, Gregorio; Marchetti, Fabio; Pineider, Francesco; Poneti, Giordano; Samaritani, Simona; Labella, Luca |
| Contributors: |
Bellucci, Luca; Fioravanti, Lorenzo; Armelao, Lidia; Bottaro, Gregorio; Marchetti, Fabio; Pineider, Francesco; Poneti, Giordano; Samaritani, Simona; Labella, Luca |
| Publisher Information: |
WILEY-V C H VERLAG GMBH |
| Publication Year: |
2023 |
| Collection: |
Padua Research Archive (IRIS - Università degli Studi di Padova) |
| Subject Terms: |
X-ray diffraction; hetero-lanthanides complexe; lanthanide; luminescence; magnetometry |
| Description: |
The similar reactivity of lanthanides generally leads to statistically populated polynuclear complexes, making the rational design of ordered hetero-lanthanide compounds extremely challenging. Here we report on the site selectivity in hetero-lanthanide tetranuclear complexes afforded by the relatively simple ditopic pyterpyNO ligand (4'-(4-pyridil)-2,2':6',2"-terpyridine N-oxide). The sequential room temperature reaction of RE2(tta)(6)(pyterpyNO)(2) (where RE=Y, (1); Eu, (2), Dy, (3) Htta=2-thenoyltrifluoroacetone) with La(tta)(3)dme (dme=dimethoxyethane) yielded Y2La2(tta)(12)(pyterpyNO)(2) (4), Dy2La2(tta)(12)(pyterpyNO)(2) (5) and Eu2La2(tta)(12)(pyterpyNO)(2) (6). Single crystals X-ray diffraction studies showed that 4, 5 and 6 are isostructural, featuring a tetranuclear structure with two different metal coordination sites with coordination numbers 8 (CN8) and 9 (CN9). The two smaller cations are mainly bridged by the O-donor atoms of the NO groups of two pyterpyNO ligands (CN8), while the larger lanthanum centres are bound by a terpyridine unit (CN9). Size selectivity has been studied with structural and magnetic studies in the solid state and through F-19 NMR and photoluminescence studies in solution, showing a direct dependence on the difference of ionic radii of the ions and yielding a 91 % selectivity for 4. Furthermore, F-19 NMR, X-ray and PL studies pointed out that the nature of the product is independent from the synthetic route for compound Eu2Y2(tta)(12)(pyterpyNO)(2) (7), keeping the ion selectivity also for a self-assembly reaction. Unexpectedly, these studies have evidenced that selectivity is not exclusively governed by electrostatic interactions related to size dimensions. |
| Document Type: |
article in journal/newspaper |
| File Description: |
ELETTRONICO |
| Language: |
English |
| Relation: |
info:eu-repo/semantics/altIdentifier/pmid/36200677; info:eu-repo/semantics/altIdentifier/wos/WOS:000890530300001; volume:29; issue:3; firstpage:e202202823; numberofpages:14; journal:CHEMISTRY-A EUROPEAN JOURNAL; https://hdl.handle.net/11577/3476089 |
| DOI: |
10.1002/chem.202202823 |
| Availability: |
https://hdl.handle.net/11577/3476089; https://doi.org/10.1002/chem.202202823 |
| Rights: |
info:eu-repo/semantics/openAccess ; license:Creative commons ; license uri:http://creativecommons.org/licenses/by/4.0/ |
| Accession Number: |
edsbas.BECC4AC9 |
| Database: |
BASE |