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Title: Chiral transcription in self-assembled tetrahedral Eu 4L 6 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 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.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [3] ; ORCiD logo [3] ;  [3] ;  [1] ;  [1]
  1. The Hong Kong Polytechnic Univ., Kowloon (Hong Kong)
  2. Durham Univ., Durham (United Kingdom)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1419458

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, and Law, Ga -Lai. Chiral transcription in self-assembled tetrahedral Eu4L6 chiral cages displaying sizable circularly polarized luminescence. United States: N. p., Web. doi:10.1038/s41467-017-01025-1.
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. Chiral transcription in self-assembled tetrahedral Eu4L6 chiral cages displaying sizable circularly polarized luminescence. United States. doi:10.1038/s41467-017-01025-1.
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, and Law, Ga -Lai. 2017. "Chiral transcription in self-assembled tetrahedral Eu4L6 chiral cages displaying sizable circularly polarized luminescence". United States. doi:10.1038/s41467-017-01025-1. https://www.osti.gov/servlets/purl/1419458.
@article{osti_1419458,
title = {Chiral transcription in self-assembled tetrahedral Eu4L6 chiral cages displaying sizable circularly polarized luminescence},
author = {Yeung, Chi -Tung and Yim, King -Him and Wong, Ho -Yin and Pal, Robert and Lo, Wai -Sum and Yan, Siu -Cheong and Yee-Man Wong, Melody and Yufit, Dmitry and Smiles, Danil E. and McCormick, Laura J. and Teat, Simon J. and Shuh, David K. and Wong, Wing -Tak and Law, Ga -Lai},
abstractNote = {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.},
doi = {10.1038/s41467-017-01025-1},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {10}
}

Works referenced in this record:

Crystal structure refinement with SHELXL
journal, January 2015
  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218