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

Autor: Zovko C; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany., Schoo C; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany., Feuerstein TJ; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany., Münzfeld L; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany., Knöfel ND; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany., Lebedkin S; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany., Kappes MM; Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.; Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg. 2, 76131, Karlsruhe, Germany., Roesky PW; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstraße 15, 76131, Karlsruhe, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Nov 02; Vol. 27 (61), pp. 15119-15126. Date of Electronic Publication: 2021 Sep 29.
DOI: 10.1002/chem.202102243
Abstrakt: 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 }(L n )] (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. P) and a high steric demand, is highly promising for the construction of advanced metal and main group complexes.
(© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: