Enantiopure Calcium Iminophosphonamide Complexes: Synthesis, Photoluminescence, and Catalysis.

Autor: Goswami B; 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., Yadav R; Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131, Karlsruhe, Germany., Köppe R; 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 Mar 01; Vol. 27 (13), pp. 4401-4411. Date of Electronic Publication: 2021 Feb 02.
DOI: 10.1002/chem.202004833
Abstrakt: The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L-H (L=[Ph 2 P{N(R)CH(CH 3 )Ph} 2 ]), L'-H (L'=[Ph 2 P{NDipp}{N(R)CH(CH 3 )Ph}]), (Dipp=2,6- i Pr 2 C 6 H 3 ), and L''-H (L''=[Ph 2 P{N(R)CH(CH 3 )naph} 2 ]), (naph=naphthyl) is presented. The resulting structures [L 2 Ca], [L' 2 Ca], and [L'' 2 Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue-green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [L'' 2 Ca] is assigned to the fluorescence of naphthyl groups, the PL of [L 2 Ca] and [L' 2 Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5-295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.
(© 2020 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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