Tilman Köhler, Pascal Marx, André Jung, Maximilian Hartmann, Jasmin Seibert, Olaf Fuhr, Eli Zysman-Colman, Stefan Bräse. “Phenonium-ion-mediated skeletal editing of paracyclophanes.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007500/v1

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Side-product fraction from the reaction of pCp alcohol 3 with one equivalent of thiophenol
NMR, DOSY NMR, and SEC Not a discrete compound, but an oligomeric mixture composed of pCp-derived units
Main, p. 6
Product mixture 11b
¹³C NMR, o/p ratio 7:2
Main, p. 7
Product mixture 11c
¹³C NMR, o/p ratio 7:3
Main, p. 7
[3.2]Paracyclophane alcohol 17
Single-crystal X-ray diffraction Hydroxymethyl group installed at the three-carbon bridge
Main, p. 9
TADF emitter 28, 10 wt% doped film in DPEPO
Photoluminescence, λexc = 360 nm Sky-blue emission, λPL = 486 nm
Photoluminescence quantum yield, ΦPL, under nitrogen 97 %
Photoluminescence quantum yield, ΦPL, in air 85 %
S1 2.93 eV
T1 2.81 eV
ΔEST 0.12 eV
Delayed emission lifetime 352 µs
Main, pp. 9–10
Reaction of pCp alcohol 3 and thiophenol with BF3·OEt2
In-situ ¹H NMR spectroscopy The starting-material and product profiles displayed an induction period and sigmoidal kinetics
Main, p. 11
pCp alcohol 3 with BF3·OEt2
¹¹B NMR δB = 0.05 ppm
¹⁹F NMR δF = −152.6 ppm
Main, p. 11
pCp alcohol 3 with BF3·OEt2 and 0.35 equivalents of water
¹¹B NMR δB = 0.01 and −1.01 ppm
¹⁹F NMR δF = −150.5 and −153.5 ppm
Main, p. 11
Reaction mixture sampled after three hours
¹¹B NMR δB = 0.01 and −1.01 ppm
¹⁹F NMR δF = −150.6 and −153.6 ppm
Main, p. 11
Reaction of pCp alcohol 3 and thiophenol with BF3·OEt2 and 0.35 equivalents of added water
In-situ ¹H NMR spectroscopy The induction period was effectively eliminated and both substrate consumption and product formation were accelerated
Main, p. 11
[3.2]Paracyclophane thioether 31
Coupling-constant analysis 10.5 Hz; anti relationship between the apical proton and the benzylic proton