Creating optically pure metal assemblies is a hot research topic in the realms of chiral supramolecules. Here, three new triple-stranded europium(iii) helicates EuL(L') [L = 4,4'-bis(4,4,4-trifluoro-1,3-dioxobutyl)diphenyl sulphide; L' = 1,10-phenanthroline (Phen) or /-2,2'-bis(diphenylphosphinyl)-1,1'-binaphthyl (/-BINAPO)] were synthesized in order to investigate the effects of ancillary ligands on controlling the stereoselective self-assembly of lanthanide helicates. X-ray single crystal structure analysis showed that EuL(Phen) crystalized in an achiral space group 1̄ with the equivalent amount of P and M helicates in one single cell. The isolated EuL(-BINAPO) and EuL(-BINAPO) were verified to be enantiopure by H, F, P NMR and DOSY NMR analyses. Additionally, the mirror-image CD spectra also demonstrated the successful syntheses of the enantiomers and the presence of an effective chirality transformation from BINAPO to achiral L. Furthermore, the perfect mirror-image circularly polarized luminescence (CPL) spectra of EuL(-BINAPO) and EuL(-BINAPO) indicated the existence of the excited state chirality of the Eu center associated with | | values reaching 0.112. In addition, the photophysical properties of three helicates were also discussed.
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| http://dx.doi.org/10.1039/d1ra01583d | DOI Listing |
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