| NMR, DOSY NMR, and SEC | The analyses indicated that the side product was not a discrete compound, but an oligomeric mixture composed of pCp-derived units |
|---|
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/v2
The main paper refers to supporting information, but no separate supporting information file was found among the files available from the ChemRxiv record
| Identifier | 17 |
|---|---|
| Single-crystal X-ray diffraction | Regioselective installation of the hydroxymethyl group at the three-carbon bridge was confirmed |
| SC-XRD CCDC deposition number | 2576565 |
| Identifier | 28 |
|---|---|
| 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 |
| In-situ ¹H NMR spectroscopy | The starting-material and product profiles displayed an induction period and sigmoidal kinetics |
|---|---|
| In-situ ¹H NMR spectroscopy with 0.35 equivalents of added water | The induction period was effectively eliminated and both substrate consumption and product formation were accelerated |
| pCp alcohol 3 with BF₃·OEt₂ (1:1), ¹¹B NMR | δB = 0.05 ppm |
|---|---|
| pCp alcohol 3 with BF₃·OEt₂ (1:1), ¹⁹F NMR | δF = −152.6 ppm |
| pCp alcohol 3 with BF₃·OEt₂ and H₂O (1:1:0.35), ¹¹B NMR | δB = 0.01 and −1.01 ppm |
| pCp alcohol 3 with BF₃·OEt₂ and H₂O (1:1:0.35), ¹⁹F NMR | δF = −150.5 and −153.5 ppm |
| Reaction mixture after 3 h, ¹¹B NMR | δB = 0.01 and −1.01 ppm |
| Reaction mixture after 3 h, ¹⁹F NMR | δF = −150.6 and −153.6 ppm |
| In-situ ¹¹B and ¹⁹F NMR spectroscopy | The newly formed species was assigned to BF₃·H₂O and formed progressively over the course of the reaction |
| Identifier | 30a |
|---|---|
| Single-crystal X-ray diffraction | Relative configuration assigned as the Felkin diastereomer |
| SC-XRD CCDC deposition number | 2576568 |
| Identifier | 31 |
|---|---|
| Coupling-constant analysis | 10.5 Hz; anti relationship between the apical proton and the benzylic proton |