Ligand Chirality Transfer from Solution State to the Crystalline Self‐Assemblies in Circularly Polarized Luminescence (CPL) Active Lanthanide Systems

Author:

Caffrey David F.1,Gorai Tumpa1,Rawson Bláithín1,Martínez‐Calvo Miguel2,Kitchen Jonathan A.3,Murray Niamh S.1,Kotova Oxana14,Comby Steve1,Peacock Robert D.5,Stachelek Patrycja6,Pal Robert6,Gunnlaugsson Thorfinnur14ORCID

Affiliation:

1. School of Chemistry and Trinity Biomedical Sciences Institute (TBSI) Trinity College Dublin The University of Dublin Dublin 2 Ireland

2. Departamento de Química Inorgánica, Facultade de Química Campus Vida Universidade de Santiago de Compostela Santiago de Compostela 15782 Spain

3. Chemistry, Institute of Natural and Mathematical Sciences Massey University Auckland 0632 New Zealand

4. AMBER (Advanced Materials and Bioengineering Research) Centre Trinity College Dublin The University of Dublin Dublin 2 Ireland

5. School of Chemistry University of Glasgow Glasgow G12 8QQ Scotland

6. Department of Chemistry Durham University Durham DH1 3LE UK

Abstract

AbstractThe synthesis of a family of chiral and enantiomerically pure pyridyl‐diamide (pda) ligands that upon complexation with europium [Eu(CF3SO3)3] result in chiral complexes with metal centered luminescence is reported; the sets of enantiomers giving rise to both circular dichroism (CD) and circularly polarized luminescence (CPL) signatures. The solid‐state structures of these chiral metallosupramolecular systems are determined using X‐ray diffraction showing that the ligand chirality is transferred from solution to the solid state. This optically favorable helical packing arrangement is confirmed by recording the CPL spectra from the crystalline assembly by using steady state and enantioselective differential chiral contrast (EDCC) CPL Laser Scanning Confocal Microscopy (CPL‐LSCM) where the two enantiomers can be clearly distinguished.

Funder

Science Foundation Ireland

Irish Research Council

Trinity College Dublin

Biotechnology and Biological Sciences Research Council

Horizon 2020 Framework Programme

Engineering and Physical Sciences Research Council

Royal Society

Irish Research Council for Science, Engineering and Technology

Publisher

Wiley

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