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Unique Double and Triple Decker Arrangements of Rare‐Earth 9,10‐Diborataanthracene Complexes Featuring Single‐Molecule Magnet Characteristics

Uhlmann, Cedric 1; Münzfeld, Luca 1; Hauser, Adrian 1; Ruan, Ting-Ting 2; Kumar Kuppusamy, Senthil ORCID iD icon 3; Jin, Chengyu 2; Ruben, Mario 2,3; Fink, Karin ORCID iD icon 2; Moreno-Pineda, Eufemio; Roesky, Peter W. 1
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
2 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)
3 Institut für QuantenMaterialien und Technologien (IQMT), Karlsruher Institut für Technologie (KIT)

Abstract:

Herein, we present the first report on the synthesis of rare-earth complexes featuring a 9,10-diborataanthracene ligand. This 14-π-electron ligand is highly reductive and was previously used in small-molecule activation. Salt elimination reactions between dipotassium 9,10-diethyl-9,10-diborataanthracene [K$_2$(DEDBA)] and [Ln$^{III}$(η$^8$-Cot$^{TIPS}$)(BH$_4$)(thf)$_x$] (Cot$^{TIPS}$=1,4-($^i$Pr$_3$Si)$_2$C$_8$H$_6$) in a 1 : 1 ratio yielded heteroleptic sandwich complexes [K(η$^8$-Cot$^{TIPS}$)Ln$^{III}$(η$^6$-DEDBA)] (Ln=Y, Dy, Er). These compounds form Lewis-base-free one-dimensional coordination polymers when crystallised from toluene. In contrast, reaction of [K$_2$(DEDBA)] and [Ln$^{III}$(η$^8$-Cot$^{TIPS}$)(BH$_4$)(thf)$_x$] in a 1 : 2 ratio led to the formation of heteroleptic triple-decker complexes [(η$^8$-Cot$^{TIPS}$)Ln$^{III}$(μ-η$^6$:η$^6$-DEDBA)Ln$^{III}$(η$^8$-Cot$^{TIPS}$)] (Ln=Y, Dy, Er). Notably, these are not only the first lanthanide triple-decker compounds featuring a six-membered ring as a deck but also the first trivalent lanthanide triple-decker featuring a heterocycle in the coordination sphere. Magnetic investigations reveal that [K(η$^8$-Cot$^{TIPS}$)Ln$^{III}$(η$^6$-DEDBA)] (Ln=Dy, Er) and [(η$^8$-Cot$^{TIPS}$)Er$^{III}$(μ-η$^6$:η$^6$-DEDBA)Er$^{III}$(η$^8$-Cot$^{TIPS}$)] exhibit Single-Molecule Magnet (SMM) behaviour. ... mehr


Verlagsausgabe §
DOI: 10.5445/IR/1000169994
Veröffentlicht am 19.04.2024
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Institut für Nanotechnologie (INT)
Institut für QuantenMaterialien und Technologien (IQMT)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 22.04.2024
Sprache Englisch
Identifikator ISSN: 1433-7851, 0570-0833, 1521-3773
KITopen-ID: 1000169994
HGF-Programm 47.12.02 (POF IV, LK 01) Exploratory Qubits
Erschienen in Angewandte Chemie - International Edition
Verlag John Wiley and Sons
Band 63
Heft 17
Seiten Art.-Nr.: e202401372
Vorab online veröffentlicht am 23.02.2024
Schlagwörter coordination chemistry, boron chemistry, heterocycle, lanthanides, triple-decker complexes
Nachgewiesen in Scopus
Web of Science
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