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Alkali Metal Complexes of a Bis(diphenylphosphino)methane Functionalized Amidinate Ligand: Synthesis and Luminescence

Zovko, Christina; Schoo, Christoph; Feuerstein, Thomas J.; Münzfeld, Luca; Knöfel, Nicolai D.; Lebedkin, Sergei; Kappes, Manfred M.; Roesky, Peter W.


A novel bis(diphenylphosphino)methane (DPPM) functionalized amidine ligand (DPPM−C(N-Dipp)$_{2}$H) (Dipp=2,6-diisopropylphenyl) was synthesized. Subsequent deprotonation with suitable alkali metal bases resulted in the corresponding complexes [M{DPPM−C(N-Dipp)$_{2}$}(Ln)] (M=Li, Na, K, Rb, Cs; L=thf, Et$_{2}$O). The alkali metal complexes form monomeric species in the solid state, exhibiting intramolecular metal-π-interactions. In addition, a caesium derivative [Cs{PPh$_{2}$CH$_{2}$-C(N-Dipp)$_{2}$}]$_{6}$ was obtained by cleavage of a diphenylphosphino moiety, forming an unusual six-membered ring structure in the solid state. All complexes were fully characterized by single crystal X-ray diffraction, NMR spectroscopy, IR spectroscopy as well as elemental analysis. Furthermore, the photoluminescent properties of the complexes were thoroughly investigated, revealing differences in emission with regards to the respective alkali metal. Interestingly, the hexanuclear [Cs{PPh$_{2}$CH$_{2}$-C(N-Dipp)$_{2}$}]$_{6}$ metallocycle exhibits a blue emission in the solid state, which is significantly red-shifted at low temperatures. The bifunctional design of the ligand, featuring orthogonal donor atoms (N vs. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000138688
Veröffentlicht am 07.10.2021
DOI: 10.1002/chem.202102243
Zitationen: 1
Web of Science
Zitationen: 3
Zitationen: 2
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 02.11.2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000138688
HGF-Programm 43.31.01 (POF IV, LK 01) Multifunctionality Molecular Design & Material Architecture
Erschienen in Chemistry - A European Journal
Verlag John Wiley and Sons
Band 27
Heft 61
Seiten 15120-15127
Nachgewiesen in Scopus
Web of Science
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