Chiral transcription in self-assembled tetrahedral Eu4L6 chiral cages displaying sizable circularly polarized luminescence

Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with differen...

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Bibliographic Details
Published in:Nature communications 2017-10, Vol.8 (1), p.1-10, Article 1128
Main Authors: Yeung, Chi-Tung, Yim, King-Him, Wong, Ho-Yin, Pal, Robert, Lo, Wai-Sum, Yan, Siu-Cheong, Yee-Man Wong, Melody, Yufit, Dmitry, Smiles, Danil E., McCormick, Laura J., Teat, Simon J., Shuh, David K., Wong, Wing-Tak, Law, Ga-Lai
Format: Article
Language:English
Subjects:
639/624/399
639/638/541/966
639/638/911
Cages
Chirality
Circular polarization
Emissivity
Europium
Humanities and Social Sciences
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Isomers
Ligands
Luminescence
multidisciplinary
Nonlinear systems
Nonlinearity
Optical properties
Science
Science (multidisciplinary)
Self-assembly
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Summary:Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with different point chiralities, and observe their self-assembly into europium (Eu) tetrametallic tetrahedral cages. One ligand exhibits a highly diastereoselective assembly into homochiral (either ΔΔΔΔ or ΛΛΛΛ) Eu tetrahedral cages whereas the two other ligands, with two different approaches of loosened point chirality, lead to a significant breakdown of the diastereoselectivity to generate a mixture of (ΔΔΔΔ and ΛΛΛΛ) isomers. The cages are highly emissive (luminescence quantum yields of 16(1) to 18(1)%) and exhibit impressive circularly polarized luminescence properties (| g lum |: up to 0.16). With in-depth studies, we present an example that correlates the nonlinear enhancement of the chiroptical response to the nonlinearity dependence on point chirality. Controlling the chirality of self-assembled polyhedra is a synthetic challenge. Here, the authors stereoselectively form emissive lanthanide tetrahedral cages from a series of chiral ligands, and use their circularly polarized luminescence to explore the effect of ligand point chirality on supramolecular architecture.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-017-01025-1