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Chiral Au(I)-NHC complexes: Manipulating TPE chirality in crystals via solvent-cooperative chiral transfer
Debin Fu‡, Yijie Zou‡, Shanting Liu, Zhao Chen*, Sheng Hua Liu*
https://doi.org/10.1016/j.cjsc.2026.101047
Circularly polarized luminescence; Homochiral tetraphenylethylene; Au(I) N-heterocyclic carbene complexes; Solvated polymorphs
ABSTRACT
A series of tetraphenylethylene (TPE)-functionalized chiral Au(I) N-heterocyclic carbene (NHC) complexes (R/S-1 to R/S-4) were designed and synthesized. A novel solvent-cooperative chiral transfer strategy was established to precisely manipulate the helical chirality of TPE moieties in crystals. Efficient intramolecular chiral transfer from chiral NHC to TPE was achieved in dilute solutions. Meanwhile, these complexes exhibited aggregation-induced circularly polarized luminescence (CPL) in THF/H2O mixtures. By varying crystallization solvents, the identical chiral NHC could induce opposite P- or M-helical conformations of TPE, in which achiral solvent molecules acted as chiral transfer mediators and stabilized the chiral conformations of TPE through weak intermolecular interactions with host molecules. Impressively, the dichloromethane co-crystals of R/S-4 containing four homochiral TPE units showed outstanding CPL performance with a |glum| value of 2.1×10-2 and a photoluminescence quantum yield exceeding 69%, benefiting from the effective locking of TPE chirality via C-H···F interactions with PF6- anions. This work reveals the synergistic mechanism of solvents in solid-state chiral transfer and provides a concise and efficient approach for constructing high-performance CPL crystalline materials.
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CN 35–1112/TQ, ISSN 0254–5861, Online ISSN: 2949-768X Copyright @ 2022 Chinese Journal of Structural Chemistry-www.Chinese Journal of Structural Chemistry.net. All Rights Reserved 闽ICP备2022002645号-1