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Enantiopure Calcium Iminophosphonamide Complexes : Synthesis, Photoluminescence, and Catalysis

Goswami, Bhupendra 1; Feuerstein, Thomas J. 1; Yadav, Ravi 1; Köppe, Ralf 1; Lebedkin, Sergei 2; Kappes, Manfred M. 2,3; 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 Physikalische Chemie (IPC), Karlsruher Institut für Technologie (KIT)


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.

Verlagsausgabe §
DOI: 10.5445/IR/1000135347
Veröffentlicht am 14.07.2021
DOI: 10.1002/chem.202004833
Zitationen: 8
Zitationen: 8
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Institut für Organische Chemie (IOC)
Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 01.03.2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000135347
HGF-Programm 43.21.04 (POF III, LK 01) Molecular Engineering
Erschienen in Chemistry - a European journal
Verlag John Wiley and Sons
Band 27
Heft 13
Seiten 4401–4411
Vorab online veröffentlicht am 23.12.2020
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