Dataset of Acetylene Derivatives of Cationic Diazaoxatriangulenes and Diaza [4]Helicenes – Access to Red Emitters and Planar Chiral Stereochemical Traits

Cationic triangulenes, and related helicenes, constitute a rich class of dyes and fluorophores, usually absorbing and emitting light at low energy, in the orange to red domains. Recently, to broaden the scope of applications, regioselective late-stage functionalizations on these core moieties have been developed. For instance, with the introduction of electron-donating groups (EDGs), important bathochromic shifts are observed pushing absorptions towards or in the near-infrared (NIR) spectral domain while emissive properties disappear essentially completely. Herein, to upset this drawback, acetylene derivatives of cationic diazaoxa triangulenes (DAOTA) and [4]helicenes are prepared (16 examples). Contrary to other EDG-functionalized derivatives, C≡C-functionalized products remain broadly fluorescent, with red-shifted absorptions (DELTA lambda abs up to 25 nm) and emissions (DELTA lambda em up to 73 nm, PHI PL up to 51%). Quite interestingly, a general dynamic stereoisomerism phenomenon is evidenced for the compounds derived from achiral DAOTA cores. At low temperature in 1H-NMR spectroscopy (218 K), N-CH2 protons become diastereotopic with chemical shifts differences (DELTA delta) as high as +1.64 ppm. The signal coalescence occurs around 273 K with a barrier of ~12 kcal.mol-1. This phenomenon is due to planar chiral conformations (Sp and Rp configurations), induced by the geometry of the alkyl (propyl) side-chains next to the acetylenic substituents. Ion pairing studies with DELTA-TRISPHAT anion not only confirm the occurrence of the chiral conformations but evidence a moderate but definite asymmetric induction from the chiral anion onto the cations. Finally, DFT calculations offer a valuable insight on the geometries, the corresponding stereodynamics and also on the very large difference in NMR for some of the diastereotopic protons.

    Organizational unit
    Laboratory of Professor Jérôme Lacour
    Creative Commons Attribution 4.0 International
    Cationic, Helicenes, •, NIR, dyes, and, fluorophores, •, Planar, chirality, •, Stereodynamics, •, Triangulenium, cations, •, VT-NMR
Publication date26/11/2021
Retention date13/01/2032
accessLevelPublicAccess levelPublic
duaNoneContract on the use of data
  • Ondrisek, Pavol orcid
  • Elie, Margaux orcid
  • Pupier, Marion orcid
  • de Aguirre, Adiran
  • Poblador Bahamonde, Amalia orcid
  • Besnard, Céline orcid
  • Lacour, Jérôme orcid
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