We herein demonstrate the synthesis of a pair of enantiomerically pure Yb^(III) complexes by post-functionalisation of the parent Yb^(III) complex via condensation with an enantiomerically pure chiral amine.The enanti...We herein demonstrate the synthesis of a pair of enantiomerically pure Yb^(III) complexes by post-functionalisation of the parent Yb^(III) complex via condensation with an enantiomerically pure chiral amine.The enantiomeric pair is structurally characterised by single crystal and powder X-ray diffraction,showing that it crystalises in the P2_(1)2_(1)2_(1) Sohncke space group with Flack parameters close to zero,which confirms their enantiopurity.Circular Dichroism(CD)and absorption spectroscopies in the NIR reveal sharp ^(2)F_(7/2)→^(2)F_(5/2) f-f transitions,with gabs values up to 0.07,indicating a chiral environment for the ytterbium centre.Furthermore,a dynamic mechanism with mixing of ligand states is shown to contribute to the CD intensity.X-band pulse Electron Paramagnetic Resonance spectroscopy,on a magnetically dilute single crystal containing 1%of Yb^(III) complexes within the isostructural YIII diamagnetic host,reveals a phase memory time,Tm,of the electronic spin of 600 ns and that it can be coherently manipulated by microwave pulses,as evidenced by Rabi nutations.展开更多
基金Novo Nordisk Foundation for research grants NNF20OC0065610 Project Grants in the Natural and Technical Sciences 2020,NNF21OC0068806 Research Infrastructure-Large equipment and facilities 2021 financing the Copenhagen Pulse-EPR FacilityNNF21OC0070832 Exploratory Inter-disciplinary Synergy Programme 2021 and NNF23OC0083201 NERD-New Exploratory Research and Discovery 2023BBSRC(BB/R013780/1)for funding.
文摘We herein demonstrate the synthesis of a pair of enantiomerically pure Yb^(III) complexes by post-functionalisation of the parent Yb^(III) complex via condensation with an enantiomerically pure chiral amine.The enantiomeric pair is structurally characterised by single crystal and powder X-ray diffraction,showing that it crystalises in the P2_(1)2_(1)2_(1) Sohncke space group with Flack parameters close to zero,which confirms their enantiopurity.Circular Dichroism(CD)and absorption spectroscopies in the NIR reveal sharp ^(2)F_(7/2)→^(2)F_(5/2) f-f transitions,with gabs values up to 0.07,indicating a chiral environment for the ytterbium centre.Furthermore,a dynamic mechanism with mixing of ligand states is shown to contribute to the CD intensity.X-band pulse Electron Paramagnetic Resonance spectroscopy,on a magnetically dilute single crystal containing 1%of Yb^(III) complexes within the isostructural YIII diamagnetic host,reveals a phase memory time,Tm,of the electronic spin of 600 ns and that it can be coherently manipulated by microwave pulses,as evidenced by Rabi nutations.
