| Melting point | 171–172 °C |
|---|---|
| ¹H NMR (400 MHz, CDCl₃) | δ 7.58 – 7.51 (m, 2H), 7.19 – 7.11 (m, 2H), 6.09 (s, 1H), 2.65 (s, 3H), 2.54 (s, 3H), 2.46 (s, 3H), 2.44 (s, 3H), 2.31 (s, 3H), 1.15 (s, 21H) |
| ¹³C {¹H} NMR (100 MHz, CDCl₃) | δ 154.5, 151.7, 141.8, 141.6, 136.9, 134.2, 133.0 (2C), 132.2, 130.4, 122.4, 121.8 (2C), 107.1, 91.3, 18.8, 17.6, 17.0, 15.5, 14.7, 13.3, 11.5 |
| ¹¹B {¹H} NMR (128 MHz, CD₂Cl₂) | δ 0.7 |
Matthieu Hicguet, Mathilde Lebreton, Brewen Le Floch, Nicolas Richy, Olivier Mongin, Thierry Roisnel, Barbara Le Grel, Fabienne Berrée, Yann Trolez. “Efficient and reversible boron coordination in a fluorescent BODIPY rotaxane.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007774/v1
| Melting point | 205–206 °C |
|---|---|
| ¹H NMR (400 MHz, CDCl₃) | δ 7.58–7.53 (m, 2H), 7.18–7.12 (m, 2H), 2.67 (s, 3H), 2.62 (s, 3H), 2.48 (s, 3H), 2.46 (s, 3H), 2.32 (s, 3H), 1.15 (s, 21H) |
| ¹³C {¹H} NMR (100 MHz, CDCl₃) | δ 154.1, 153.5, 141.5, 141.2, 138.6, 134.0, 133.5, 132.9, 132.1 (2C), 130.2, 122.6, 106.8, 91.4, 84.8, 19.6, 18.7, 17.6, 15.9, 15.6, 13.4, 11.3 |
| ¹¹B {¹H} NMR (128 MHz, CD₂Cl₂) | δ 0.7 |
| HRMS (ESI+) | [M]⁺˙ calcd for C₃₁H₄₀¹¹BF₂N₂Si: 644.2061; found: 644.2067 |
| NMR spectra (¹H, 400 MHz, CDCl₃; ¹³C {¹H}, 100 MHz, CDCl₃; ¹¹B {¹H}, 128 MHz, CD₂Cl₂) | Image data were not transcribed |
| Melting point | 283–285 °C (gradual darkening before melting) |
|---|---|
| ¹H NMR (600 MHz, CDCl₃) | δ 7.56 (d, J = 7.9 Hz, 4H), 7.18 (d, J = 8.1 Hz, 4H), 2.71 (s, 3H), 2.49 (s, 6H), 2.34 (s, 6H), 1.15 (s, 42H) |
| ¹³C {¹H} NMR (100 MHz, CDCl₃) | δ 152.5, 142.1, 137.3, 134.0, 133.2, 132.5, 132.2, 130.4, 122.5, 107.0, 91.4, 18.8, 17.4, 15.6, 13.4, 11.5 |
| ¹¹B {¹H} NMR (128 MHz, CDCl₃) | δ 0.8 |
| HRMS (ESI+) | [M]⁺˙ calcd for C₄₈H₆₅¹¹BF₂N₂Si₂: 774.4741; found: 774.4748 |
| NMR spectra (¹H, 600 MHz, CDCl₃; ¹³C {¹H}, 100 MHz, CDCl₃; ¹¹B {¹H}, 128 MHz, CD₂Cl₂) | Image data were not transcribed |
| ¹H NMR (400 MHz, CDCl₃) | δ 7.52–7.46 (m, 6H), 7.38 (d, J = 8.8 Hz, 4H), 7.34 (dd, J = 7.6, 1.6 Hz, 2H), 7.11 (t, J = 7.7 Hz, 2H), 7.00 (d, J = 8.8 Hz, 4H), 6.89 (d, J = 8.1 Hz, 4H), 6.77 (d, J = 8.8 Hz, 4H), 6.57 (d, J = 8.8 Hz, 4H), 4.06 (t, J = 6.1 Hz, 4H), 3.76 (t, J = 5.9 Hz, 4H), 1.92 (brs, 8H), 1.87 (s, 3H), 1.76 (s, 6H), 1.75 (s, 6H), 1.58 (s, 6H), 1.15 (s, 42H) |
|---|---|
| ¹³C {¹H} NMR (100 MHz, CDCl₃) | δ 157.1, 156.8, 152.4, 152.2, 143.2, 141.0, 135.9, 134.7, 134.1, 133.2, 132.6, 132.0, 132.0, 131.8, 131.3, 130.4, 130.3, 129.9, 129.2, 127.6, 122.0, 121.9, 113.7, 107.2, 91.2, 66.8, 66.7, 41.5, 30.9, 25.5, 25.3, 18.9, 17.8, 15.5, 14.2, 11.5 |
| ¹¹B {¹H} NMR (128 MHz, CD₂Cl₂) | δ 3.4 |
| HRMS (ESI−) | [M−H]⁻ calcd for C₉₅H₁₀₈¹¹BN₂O₆Si₂: 1439.7844; found: 1439.7839 |
| NMR spectra (¹H, 400 MHz, CDCl₃; ¹³C {¹H}, 100 MHz, CDCl₃; ¹¹B {¹H}, 128 MHz, CDCl₃) | Image data were not transcribed |
| ¹H NMR (400 MHz, CD₂Cl₂) | δ 7.51 (d, J = 8.0 Hz, 4H) 7.49 (dd, J = 8.0, 1.6 Hz, 2H), 7.36–7.31 (m, 6H), 7.12 (t, J = 7.7 Hz, 2H), 7.03–6.99 (m, 4H), 6.95 (d, J = 8.0 Hz, 4H), 6.78 (d, J = 8.7 Hz, 4H), 6.56 (d, J = 8.7 Hz, 4H), 4.06 (t, J = 5.4 Hz, 4H), 3.76 (t, J = 6.1 Hz, 4H), 3.17 (s, 2H), 1.93–1.90 (m, 11H), 1.77 (s, 12H), 1.57 (s, 6H) |
|---|---|
| ¹³C {¹H} NMR (100 MHz, CD₂Cl₂) | δ 157.6, 157.2, 152.6, 152.5, 143.5, 141.9, 136.7, 135.5, 134.4, 133.5, 132.9, 132.47, 132.3, 132.1, 131.5, 130.8, 130.1, 129.5, 127.9, 122.2, 120.8, 114.0, 113.9, 83.8, 77.8, 67.2, 67.0, 41.7, 30.9, 25.8, 25.6, 18.2, 15.6, 14.3 |
| ¹¹B {¹H} NMR (128 MHz, CD₂Cl₂) | δ 3.4 |
| HRMS (ESI−) | [M−H]⁻ calcd for C₇₇H₆₈¹¹BN₂O₆: 1127.5176; found: 1127.5179 |
| Single-crystal X-ray diffraction | CCDC 2570222; C₇₇H₆₉BN₂O₆ + solvent; M = 1129.15 g mol⁻¹; T = 150(2) K; monoclinic; space group P 2₁/c; a = 38.865(3) Å; b = 16.0012(8) Å; c = 32.3556(17) Å; β = 95.760(5)°; V = 19796.6(19) ų; Dᶜ = 1.137 g cm⁻³; absorption coefficient = 0.071 mm⁻¹; final refinement on F² with 45345 unique intensities and 2357 parameters converged at ωR(F²) = 0.2264 (Rᶠ = 0.1217) for 29766 observed reflections with I > 2σ |
| Single-crystal X-ray diffraction data file | Data were not transcribed |
| Single-crystal X-ray structure image | Image data were not transcribed |
| NMR spectra (¹H, 400 MHz, CD₂Cl₂; ¹³C {¹H}, 100 MHz, CD₂Cl₂; ¹¹B {¹H}, 128 MHz, CD₂Cl₂) | Image data were not transcribed |
| ¹H NMR (400 MHz, CD₂Cl₂) | δ 7.85 (s, 2H), 7.83 (d, J = 8.3 Hz, 4H), 7.49 (dd, J = 7.8, 1.6 Hz, 2H), 7.36 (d, J = 8.8 Hz, 4H), 7.34 (dd, J = 7.6, 1.6 Hz, 2H), 7.28–7.24 (m, 12H), 7.19–7.14 (m, 16H), 7.12 (t, J = 7.7 Hz, 2H), 7.04 (d, J = 8.2 Hz, 4H), 7.02–6.97 (m, 4H), 6.80 (d, J = 8.8 Hz, 8H), 6.55 (d, J = 8.8 Hz, 4H), 4.62 (t, J = 6.9 Hz, 4H), 4.06 (t, J = 5.6 Hz, 4H), 4.01 (t, J = 5.7 Hz, 4H), 3.75 (t, J = 6.0 Hz, 4H), 2.43 (p, J = 6.6 Hz, 4H), 1.94 (s, 3H), 1.91 (brs, 8H), 1.80 (s, 12H), 1.54 (s, 6H), 1.29 (s, 54H) |
|---|---|
| ¹³C {¹H} NMR (150 MHz, CDCl₃) | δ 157.6, 157.1, 156.8, 152.7, 152.6, 148.8, 147.6, 144.9, 143.4, 141.5, 140.6, 136.6, 134.4, 133.5, 132.9, 132.4, 132.2, 132.1, 131.5, 131.3, 130.8 (2C), 130.1, 129.7, 129.5, 127.9, 125.8, 124.7 (2C), 122.1, 120.5, 113.9, 113.6, 67.2, 67.0, 64.6, 63.5, 47.7, 41.7, 34.6, 31.5, 31.0, 30.5, 25.7, 25.6, 15.7, 14.4 |
| ¹¹B {¹H} NMR (128 MHz, CD₂Cl₂) | δ 3.4 |
| HRMS (ESI−) | [M−H]⁻ calcd for C₁₅₇H₁₆₆¹¹BN₈O₈: 2302.2927; found: 2302.2924 |
| ¹H NMR, BODIPY methyl groups a, b and c | Strongly shielded and resonated below 2 ppm |
| UV–Vis absorption (CH₂Cl₂; average of two independent samples measured at four concentrations) | λ₁abs = 375 nm; ε₁max = 4.4 × 10³ M⁻¹ cm⁻¹; λ₂abs = 532 nm; ε₂max = 5.09 × 10⁴ M⁻¹ cm⁻¹ |
| Fluorescence (CH₂Cl₂) | λem = 577 nm; ΦF = 0.91; ΦF standard: fluorescein in 0.1 M NaOH (ΦF = 0.90 at λex = 465 nm); τ = 5.1 ns, monoexponential decay; kᵣ = 1.8 × 10⁸ s⁻¹; kₙᵣ = 1.8 × 10⁷ s⁻¹ |
| Two-photon absorption by two-photon excitation fluorescence (CH₂Cl₂) | σ₂ = 48 GM; maximum at 740 nm; the lowest-energy absorption band was essentially inactive under two-photon excitation, while a higher-energy transition corresponding to the one-photon absorption band around 380 nm gave a significant response |
| NMR spectra (¹H, 400 MHz, CD₂Cl₂; ¹³C {¹H}, 150 MHz, CD₂Cl₂; ¹¹B {¹H}, 128 MHz, CD₂Cl₂) | Image data were not transcribed |
| ¹H NMR (600 MHz, CD₂Cl₂) | δ 7.78 (s, 2H), 7.62 (d, J = 8.0 Hz, 4H), 7.37 (s, 2H), 7.35 (d, 2H), 7.33 (d, J = 8.8 Hz, 4H), 7.28 (dd, J = 7.6, 1.3 Hz, 2H), 7.25 (d, J = 8.5 Hz, 12H), 7.22 (d, J = 8.1 Hz, 4H), 7.15 (d, J = 8.5 Hz, 16H), 7.09 (t, J = 7.6 Hz, 2H), 7.06 (d, J = 8.9 Hz, 4H), 6.77 (d, J = 8.6 Hz, 4H), 6.73 (d, J = 8.8 Hz, 4H), 6.65 (d, J = 8.7 Hz, 4H), 4.36 (t, J = 7.0 Hz, 4H), 3.97 (t, J = 6.1 Hz, 4H), 3.87 (t, J = 5.6 Hz, 4H), 3.77 (t, J = 5.9 Hz, 4H), 2.75 (s, 3H), 2.46 (s, 6H), 2.36 (s, 6H), 2.25–2.21 (m, 4H), 1.87–1.75 (m, 8H), 1.56 (s, 6H), 1.30 (s, 54H) |
|---|---|
| ¹³C {¹H} NMR (100 MHz, CD₂Cl₂) | δ 158.1, 157.3, 156.8, 152.6, 150.6, 148.8, 147.2, 144.8, 143.7, 142.7, 140.6, 137.9, 134.5, 133.9, 133.5, 132.4, 131.2, 131.2, 130.8, 130.7, 130.5, 130.2, 129.6, 128.1, 127.8, 126.1, 124.7 (2C), 121.6, 120.5, 115.2, 114.2, 113.6, 67.7, 67.5, 64.5, 63.5, 47.6, 42.0, 35.0, 31.5, 31.2, 30.1, 25.8 (2C), 17.7, 15.8, 13.5 |
| ¹¹B {¹H} NMR (192 MHz, CD₂Cl₂) | δ 0.8 |
| HRMS (ESI−) | [M−H]⁻ calcd for C₁₅₇H₁₆₈¹¹BF₂N₈O₈: 2342.3052; found: 2342.3048 |
| ¹H NMR, BODIPY methyl groups a, b and c | Signals shifted downfield to 2.35–2.80 ppm |
| ¹H NMR, H-e, H-g and H-h | More shielded |
| ¹H NOESY NMR (600 MHz, CD₂Cl₂) | Several NOE correlations between macrocycle protons and thread protons were observed, including H-10/H-11 with H-g |
| UV–Vis absorption (CH₂Cl₂; average of two independent samples measured at four concentrations) | λ₁abs = 381 nm; ε₁max = 6.7 × 10³ M⁻¹ cm⁻¹; λ₂abs = 527 nm; ε₂max = 6.20 × 10⁴ M⁻¹ cm⁻¹ |
| Fluorescence (CH₂Cl₂) | λem = 573 nm; ΦF = 0.79; ΦF standard: fluorescein in 0.1 M NaOH (ΦF = 0.90 at λex = 465 nm); τ = 4.3 ns, monoexponential decay; kᵣ = 1.8 × 10⁸ s⁻¹; kₙᵣ = 4.9 × 10⁷ s⁻¹ |
| Two-photon absorption by two-photon excitation fluorescence (CH₂Cl₂) | σ₂ = 100 GM; maximum at 740 nm; twofold enhancement compared with precursor 10; the lowest-energy absorption band was essentially inactive under two-photon excitation, while a higher-energy transition corresponding to the one-photon absorption band around 380 nm gave a significant response |
| NMR spectra (¹H, 400 MHz, CD₂Cl₂; ¹³C {¹H}, 100 MHz, CD₂Cl₂; ¹¹B {¹H}, 192 MHz, CD₂Cl₂; ¹H NOESY, 600 MHz, CD₂Cl₂) | Image data were not transcribed |
| ¹H NMR spectra comparison (CD₂Cl₂) | Image data were not transcribed |
|---|---|
| UV–Vis absorption, fluorescence and two-photon absorption spectra (CH₂Cl₂) | Image data were not transcribed |
| Two-photon excitation fluorescence (700 nm), fluorescence intensity versus laser excitation power | Quadratic dependence; image data were not transcribed |