| ¹H NMR (400 MHz, DMSO-d₆) | δ = 8.20–7.70 (brs, 4H), 7.40–7.25 (brs, 2H), 7.10–6.85 (brs, 2H), 4.90–4.20 (brs, 4H); image data were not transcribed |
|---|
Ryoji Furuta, Luxia Cui, Takuro Tsutsumi, Takunori Harada, Yusuke Ishigaki, Yu Hoshino, Robert Naumann, Katja Heinze, Toshikazu Ono. “Geometric locking in B–O–B bridged helicenes: simultaneous enhancement of emission efficiency and configurational stability.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007837/v1
| ¹H NMR (400 MHz, Acetone-d₆) | δ = 8.77–8.75 (d, J = 9.3 Hz, 2H), 8.24–8.21 (m, 4H), 8.13 (S, 2H), 7.59–7.55 (m, 2H), 7.53–7.50 (d, J = 9.3 Hz, 2H), 7.32–7.27 (m, 4H); image data were not transcribed |
|---|---|
| ¹³C NMR (101 MHz, CDCl₃) | δ = 142.9, 134.6, 129.9, 128.7, 125.9, 125.1, 111.8; image data were not transcribed |
| ¹⁹F NMR (377 MHz, Acetone-d₆) | δ = –126.79 (s, 2F), (–142.56) – (–143.18) (dd, J = 162.3, 70.8 Hz, 4F); image data were not transcribed |
| ¹¹B NMR (128 MHz, CDCl₃) | δ = 3.39; image data were not transcribed |
| HRMS (FAB, positive) | m/z calcd. for C₂₆H₁₆B₄F₆N₆O₃ [M]⁺ 618.1560; found: 618.1578 |
| Elemental analysis | Calcd (%) for [1a] (C₂₆H₁₆B₄F₆N₆O₃·1.2H₂O·0.3CH₂Cl₂) (%): C, 47.52; H, 2.88; N, 12.64. Found: C, 47.61; H, 2.96; N, 12.57 |
| Melting point | > 300 °C |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 320, 400, 419 nm; λem: 467, 497 nm; ΦPL: 30 %; τav: 2.60 ns, excited at 405 nm; kr: 1.15 × 10⁸ s⁻¹; knr: 2.69 × 10⁸ s⁻¹; image data were not transcribed |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene, c = 10⁻⁶ M) | λabsmax: 368, 419 nm; λemmax, excited at λabsmax: 467, 497 nm; ΦPL, excited at 330 nm: 0.30; τav: 2.60 ns; Stokes shift: 2450, 3750 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (THF, c = 10⁻⁶ M) | λabsmax: 315, 414 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.12; τav: 1.73 ns; Stokes shift: 4110 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (DCM, c = 10⁻⁶ M) | λabsmax: 397, 416 nm; λemmax, excited at λabsmax: 498 nm; ΦPL, excited at 330 nm: 0.21; τav: 2.24 ns; Stokes shift: 3960 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (MeCN, c = 10⁻⁶ M) | λabsmax: 312, 408 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.11; τav: 1.41 ns; Stokes shift: 4470 cm⁻¹ |
| UV–vis absorption, emission and excitation spectra (various solvents, c = 10⁻⁶ M) | Image data were not transcribed |
| Time-resolved photoluminescence lifetime fit (toluene, λex = 405 nm, λem = 497 nm) | CHI: 1.18; τav: 2.60 ns; τ1: 0.46 ns; τ2: 2.58 ns; A1: −17.47; A2: 360.87 |
| Time-resolved photoluminescence lifetime fit (THF, λex = 405 nm, λem = 499 nm) | CHI: 1.18; τav: 1.73 ns; τ1: 0.03 ns; τ2: 1.70 ns; A1: −384.09; A2: 402.39 |
| Time-resolved photoluminescence lifetime fit (DCM, λex = 405 nm, λem = 498 nm) | CHI: 1.16; τav: 2.24 ns; τ1: 0.61 ns; τ2: 2.22 ns; A1: −15.28; A2: 374.78 |
| Time-resolved photoluminescence lifetime fit (MeCN, λex = 405 nm, λem = 499 nm) | CHI: 1.17; τav: 1.41 ns; τ1: 0.50 ns; τ2: 1.41 ns; A1: −10.06; A2: 428.73 |
| Time-resolved photoluminescence decay curves (various solvents) | Image data were not transcribed |
| Photoluminescence and fluorescence lifetime (2-MeTHF, c = 10⁻⁶ M, 298 K) | λemmax, excited at 415 nm: 499 nm; ΦPL, excited at 415 nm: 0.13; τav: 1.98 ns; kr: 0.66 × 10⁸ s⁻¹; knr: 4.39 × 10⁸ s⁻¹ |
| Photoluminescence and fluorescence lifetime (2-MeTHF, c = 10⁻⁶ M, 77 K) | λemmax, excited at 415 nm: 481 nm; ΦPL, excited at 415 nm: 0.43; τav: 4.17 ns; kr: 1.03 × 10⁸ s⁻¹; knr: 1.37 × 10⁸ s⁻¹ |
| Time-resolved photoluminescence lifetime fit (2-MeTHF, room temperature, λex = 405 nm, λem = 498 nm) | CHI: 1.08; τav: 1.98 ns; τ1: 1.98 ns; A1: 379.38 |
| Time-resolved photoluminescence lifetime fit (2-MeTHF, 77 K, λex = 405 nm, λem = 483 nm) | CHI: 1.04; τav: 4.17 ns; τ1: 4.17 ns; A1: 777.27 |
| Excitation, emission and decay curves (2-MeTHF, c = 10⁻⁶ M, 298 and 77 K) | Image data were not transcribed |
| CD, absorption and gabs spectra (toluene, c = 10⁻⁵ M); CPL, DC and glum spectra (toluene, c = 10⁻⁶ M, excited at 310 nm) | |glum|: 2.0 × 10⁻³; image data were not transcribed |
| Concentration-dependent UV–vis absorption and CD spectra (toluene, 25 °C, 1 cm path length) | Maximum absorbance: 0.2, 0.5, 1.2; image data were not transcribed |
| Configurational stability (toluene, 100 °C, 72 h) | More than 99 % of the initial CD intensity was retained; no changes were observed in the CD and UV–vis spectra; lower bound of the Gibbs free energy of activation at 373.15 K: 35.18 kcal mol⁻¹; image data were not transcribed |
| Transient absorption (degassed toluene, 293 K, excited at 443 nm) | Global analysis yielded four time constants; τ₃ = 2.80 ns, assigned to S₁ depopulation; τav = 2.60 ns; the long-lived τ₄ component, assigned to a T₁ state, remained constant within the observed time window; image data were not transcribed |
| Single-crystal XRD, CCDC number | 2548390 |
| Single-crystal XRD, empirical formula | C₂₈H₁₈B₄Cl₆F₆N₆O₃ |
| Single-crystal XRD, formula weight | 856.42 |
| Single-crystal XRD (150 K, λ = 0.71073 Å), crystal system and space group | triclinic; P-1 |
| Single-crystal XRD, unit cell | a = 9.3390(7) Å, α = 106.206(9)°; b = 13.8008(16) Å, β = 97.966(7)°; c = 14.7775(12) Å, γ = 106.376(8)°; V = 1705.2(3) ų; Z = 2 |
| Single-crystal XRD, calculated density | 1.668 g cm⁻³ |
| Single-crystal XRD, absorption coefficient and F(000) | 0.581 mm⁻¹; 856.0 |
| Single-crystal XRD, data collection | θ = 2.542 to 27.102°; 11600 reflections collected; 11600 independent reflections [Rint = ?; Rsigma = 0.1532] |
| Single-crystal XRD, refinement | Data/restraints/parameters: 11600/0/479; goodness-of-fit on F²: 0.869 |
| Single-crystal XRD, R indices | R1 [I > 2σ(I)] = 0.0562; wR2 (all data) = 0.2074 |
| Single-crystal XRD, largest difference peak and hole | 0.49/−0.58 e Å⁻³ |
| Single-crystal XRD, dihedral angles | C–C–C–C: 9.73(8)°; C–C–C–O: 13.04(9)° and 16.80(9)° |
| Single-crystal XRD molecular-structure image | Image data were not transcribed |
| ¹H NMR (400 MHz, Acetone-d₆) | δ = 8.75–8.73 (d, J = 9.3 Hz, 2H), 8.10 (s, 2H), 7.47–7.44 (d, J = 9.3 Hz, 2H), 7.13 (s, 2H), 7.06 (s, 2H), 2.51 (s, 6H), 2.22 (s, 6H), 1.80 (s, 6H); image data were not transcribed |
|---|---|
| ¹³C NMR (101 MHz, CDCl₃) | δ = 165.61, 142.9, 141.2, 137.3, 130.1, 128.6, 128.3, 125.6, 124.9, 121.8, 111.7, 21.5, 18.8, 18.5; image data were not transcribed |
| ¹⁹F NMR (377 MHz, CDCl₃) | δ = –129.47 (s, 2F), (–145.24)–(–145.43) (d, J = 72.1 Hz, 2F), (–145.98)–(–146.17) (d, J = 69.4 Hz, 2F); image data were not transcribed |
| ¹¹B NMR (128 MHz, CDCl₃) | δ = 3.51 (s); image data were not transcribed |
| HRMS (FAB, positive) | m/z calcd. for C₃₂H₂₈B₄F₆N₆O₃ [M]⁺ 702.2499; found: 702.2520 |
| Elemental analysis | Calcd (%) for [1b] (C₃₂H₂₈B₄F₆N₆O₃·0.5 CH₂Cl₂·0.2 hexane) (%): C, 53.15; H, 4.21; N, 11.04. Found: C, 53.16; H, 4.27; N, 11.06 |
| Melting point | > 300 °C |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 383 nm; λem: 448, 476 nm; ΦPL: 35 %; τav: 3.22 ns, excited at 365 nm; kr: 1.09 × 10⁸ s⁻¹; knr: 2.02 × 10⁸ s⁻¹; image data were not transcribed |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene, c = 10⁻⁶ M) | λabsmax: 383 nm; λemmax, excited at λabsmax: 448, 476, 500 nm; ΦPL, excited at 330 nm: 0.35; τav: 3.21 ns; Stokes shift: 3790, 5100, 6110 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (THF, c = 10⁻⁶ M) | λabsmax: 378 nm; λemmax, excited at λabsmax: 473 nm; ΦPL, excited at 330 nm: 0.10; τav: 2.65 ns; Stokes shift: 5310 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (DCM, c = 10⁻⁶ M) | λabsmax: 377 nm; λemmax, excited at λabsmax: 449, 476 nm; ΦPL, excited at 330 nm: 0.18; τav: 2.58 ns; Stokes shift: 4250, 5520 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (MeCN, c = 10⁻⁶ M) | λabsmax: 377 nm; λemmax, excited at λabsmax: 472 nm; ΦPL, excited at 330 nm: 0.15; τav: 2.35 ns; Stokes shift: 5340 cm⁻¹ |
| UV–vis absorption, emission and excitation spectra (various solvents, c = 10⁻⁶ M) | Image data were not transcribed |
| Time-resolved photoluminescence lifetime fit (toluene, λex = 365 nm, λem = 476 nm) | CHI: 1.22; τav: 3.21 ns; τ1: 0.85 ns; τ2: 3.18 ns; A1: −16.94; A2: 329.09 |
| Time-resolved photoluminescence lifetime fit (THF, λex = 365 nm, λem = 473 nm) | CHI: 1.33; τav: 2.65 ns; τ1: 0.75 ns; τ2: 2.70 ns; A1: 31.28; A2: 306.34 |
| Time-resolved photoluminescence lifetime fit (DCM, λex = 365 nm, λem = 476 nm) | CHI: 1.19; τav: 2.58 ns; τ1: 0.03 ns; τ2: 2.52 ns; A1: −668.48; A2: 336.95 |
| Time-resolved photoluminescence lifetime fit (MeCN, λex = 365 nm, λem = 472 nm) | CHI: 1.25; τav: 2.35 ns; τ1: 0.81 ns; τ2: 2.32 ns; A1: −23.02; A2: 356.92 |
| Time-resolved photoluminescence decay curves (various solvents) | Image data were not transcribed |
| CD, absorption and gabs spectra (toluene, c = 10⁻⁵ M); CPL, DC and glum spectra (toluene, c = 10⁻⁶ M, excited at 310 nm) | |glum|: 1.0 × 10⁻³; image data were not transcribed |
| Concentration-dependent UV–vis absorption and CD spectra (toluene, 25 °C, 1 cm path length) | Maximum absorbance: 0.2, 0.5, 1.2; image data were not transcribed |
| Transient absorption (degassed toluene, 293 K, excited at 444 nm) | Global analysis yielded four time constants; τ₃ = 0.34 ns, assigned to S₁ depopulation; τav = 0.35 ns; the long-lived τ₄ component, assigned to a T₁ state, remained constant within the observed time window; image data were not transcribed |
| Single-crystal XRD, CCDC number | 2549004 |
| Single-crystal XRD, empirical formula | C₃₃H₃₀B₄Cl₂F₆N₆O₃ |
| Single-crystal XRD, formula weight | 786.77 |
| Single-crystal XRD (123 K, λ = 0.71073 Å), crystal system and space group | triclinic; P-1 |
| Single-crystal XRD, unit cell | a = 8.2446(4) Å, α = 99.381(4)°; b = 14.3112(7) Å, β = 102.986(4)°; c = 15.6540(7) Å, γ = 96.770(4)°; V = 1752.63(15) ų; Z = 2 |
| Single-crystal XRD, calculated density | 1.491 g cm⁻³ |
| Single-crystal XRD, absorption coefficient and F(000) | 0.263 mm⁻¹; 804.0 |
| Single-crystal XRD, data collection | θ = 2.569 to 25.347°; 9371 reflections collected; 9371 independent reflections [Rint = ?; Rsigma = 0.0191] |
| Single-crystal XRD, refinement | Data/restraints/parameters: 9371/0/494; goodness-of-fit on F²: 1.146 |
| Single-crystal XRD, R indices | R1 [I > 2σ(I)] = 0.0548; wR2 (all data) = 0.2134 |
| Single-crystal XRD, largest difference peak and hole | 0.41/−0.50 e Å⁻³ |
| Single-crystal XRD, dihedral angles | C–C–C–C: 11.55(5)°; C–C–C–O: −81.96(5)° and −82.01(5)° |
| Single-crystal XRD molecular-structure image | Image data were not transcribed |
| ¹H NMR (400 MHz, CDCl₃) | δ = 8.25–8.23 (d, J = 9.3 Hz, 2H), 7.99–7.95 (m, 4H), 7.74 (s, 2H), 7.36–7.32 (m, 6H); image data were not transcribed |
|---|---|
| ¹⁹F NMR (377 MHz, CDCl₃) | δ = –129.16 (s, 2F), (–145.41)–(–145.61) (d, J = 72.1 Hz, 2F), (–146.29)–(–146.49) (d, J = 73.5 Hz, 2F); image data were not transcribed |
| HRMS (FAB, positive) | m/z calcd. for C₂₆H₁₄B₄Br₂F₆N₆O₃ [M]⁺ 775.9750; found: 775.9773 |
| Elemental analysis | Calcd (%) for [1c] (C₂₆H₁₄B₄Br₂F₆N₆O₃·0.2 CH₂Cl₂·0.1 hexane) (%): C, 40.18; H, 1.99; N, 10.49. Found: C, 40.10; H, 2.06; N, 10.41 |
| Melting point | > 300 °C |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 323, 401, 421 nm; λem: 468, 499 nm; ΦPL: 24 %; τav: 2.01 ns, excited at 405 nm; kr: 1.19 × 10⁸ s⁻¹; knr: 3.78 × 10⁸ s⁻¹; image data were not transcribed |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene, c = 10⁻⁶ M) | λabsmax: 323, 421 nm; λemmax, excited at λabsmax: 468, 499 nm; ΦPL, excited at 330 nm: 0.24; τav: 2.00 ns; Stokes shift: 2390, 3710 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (THF, c = 10⁻⁶ M) | λabsmax: 318, 416 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.11; τav: 1.56 ns; Stokes shift: 4000 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (DCM, c = 10⁻⁶ M) | λabsmax: 319, 418 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.17; τav: 1.86 ns; Stokes shift: 3880 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (MeCN, c = 10⁻⁶ M) | λabsmax: 316, 413 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.10; τav: 1.35 ns; Stokes shift: 4170 cm⁻¹ |
| UV–vis absorption, emission and excitation spectra (various solvents, c = 10⁻⁶ M) | Image data were not transcribed |
| Time-resolved photoluminescence lifetime fit (toluene, λex = 405 nm, λem = 499 nm) | CHI: 1.12; τav: 2.00 ns; τ1: 0.69 ns; τ2: 1.99 ns; A1: −11.41; A2: 381.19 |
| Time-resolved photoluminescence lifetime fit (THF, λex = 405 nm, λem = 499 nm) | CHI: 1.31; τav: 1.56 ns; τ1: 0.48 ns; τ2: 1.55 ns; A1: −17.41; A2: 412.00 |
| Time-resolved photoluminescence lifetime fit (DCM, λex = 405 nm, λem = 499 nm) | CHI: 1.13; τav: 1.86 ns; τ1: 0.73 ns; τ2: 1.86 ns; A1: −5.86; A2: 389.55 |
| Time-resolved photoluminescence lifetime fit (MeCN, λex = 405 nm, λem = 499 nm) | CHI: 1.04; τav: 1.35 ns; τ1: 0.15 ns; τ2: 1.34 ns; A1: −57.78; A2: 432.53 |
| Time-resolved photoluminescence decay curves (various solvents) | Image data were not transcribed |
| CD, absorption and gabs spectra (toluene, c = 10⁻⁵ M); CPL, DC and glum spectra (toluene, c = 10⁻⁶ M, excited at 330 nm) | |glum|: 1.5 × 10⁻³; image data were not transcribed |
| Concentration-dependent UV–vis absorption and CD spectra (toluene, 25 °C, 1 cm path length) | Maximum absorbance: 0.2, 0.5, 1.2; image data were not transcribed |
| Single-crystal XRD, CCDC number | 2549005 |
| Single-crystal XRD, empirical formula | C₂₇H₁₆B₄N₆O₃F₆Cl₂Br₂ |
| Single-crystal XRD, formula weight | 860.42 |
| Single-crystal XRD (150 K, λ = 1.54184 Å), crystal system and space group | monoclinic; Ia |
| Single-crystal XRD, unit cell | a = 9.66616(8) Å, α = 90°; b = 22.87622(17) Å, β = 97.9229(7)°; c = 14.37347(11) Å, γ = 90°; V = 3148.00(4) ų; Z = 4 |
| Single-crystal XRD, calculated density | 1.815 g cm⁻³ |
| Single-crystal XRD, absorption coefficient and F(000) | 5.543 mm⁻¹; 1688.0 |
| Single-crystal XRD, data collection | θ = 3.657 to 77.293°; 26108 reflections collected; 5536 independent reflections [Rint = 0.0368; Rsigma = 0.0220] |
| Single-crystal XRD, refinement | Data/restraints/parameters: 5536/2/451; goodness-of-fit on F²: 1.045 |
| Single-crystal XRD, R indices | R1 [I > 2σ(I)] = 0.0441; wR2 (all data) = 0.1232 |
| Single-crystal XRD, largest difference peak and hole | 0.68/−0.50 e Å⁻³ |
| Single-crystal XRD, dihedral angles | C–C–C–C: 11.60(6)°; C–C–C–O: −20.70(8)° and −17.50(8)° |
| Single-crystal XRD molecular-structure image | Image data were not transcribed |
| ¹H NMR (400 MHz, Acetone-d₆) | δ = 8.79–8.76 (d, J = 9.3 Hz, 2H), 8.14 (s, 2H), 7.95–7.93 (d, J = 8.8 Hz, 4H), 7.77–7.75 (d, J = 8.7 Hz, 4H), 7.53–7.51 (d, J = 9.3 Hz, 2H) |
|---|---|
| ¹⁹F NMR (377 MHz, Acetone-d₆) | δ = –127.48 (s, 2F), (–142.42)–(–142.61) (d, J = 70.8 Hz, 2F), (–143.48)–(–143.68) (d, J = 72.1 Hz, 2F) |
| NMR spectra | Image data were not transcribed |
| HRMS (FAB, positive) | m/z calcd. for C₂₆H₁₄B₄F₆I₂N₆O₃ [M]⁺ 869.9493; found: 869.9511 |
| Elemental analysis | Calcd (%) for [1d] (C₂₆H₁₄B₄I₂F₆N₆O₃·0.3 hexane) (%): C, 37.29; H, 2.05; N, 9.39. Found: C, 37.63; H, 2.22; N, 9.82 |
| Melting point | > 300 °C |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 328, 423, 447 nm; λem: 470, 499 nm; ΦPL: 5 %; τav: 0.35 ns, excited at 405 nm; kr: 1.43 × 10⁸ s⁻¹; knr: 27.14 × 10⁸ s⁻¹; image data were not transcribed |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene, c = 10⁻⁶ M) | λabsmax: 328, 423 nm; λemmax, excited at λabsmax: 470, 499 nm; ΦPL, excited at 330 nm: 0.05; τav: 0.32 ns; Stokes shift: 2360, 3600 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (THF, c = 10⁻⁶ M) | λabsmax: 322, 419 nm; λemmax, excited at λabsmax: 500 nm; ΦPL, excited at 330 nm: 0.03; τav: 0.35 ns; Stokes shift: 3870 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (DCM, c = 10⁻⁶ M) | λabsmax: 323, 419 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.04; τav: 0.32 ns; Stokes shift: 3830 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (MeCN, c = 10⁻⁶ M) | λabsmax: 320, 415 nm; λemmax, excited at λabsmax: 499 nm; ΦPL, excited at 330 nm: 0.03; τav: 0.30 ns; Stokes shift: 4060 cm⁻¹ |
| UV–vis absorption, emission and excitation spectra (various solvents, c = 10⁻⁶ M) | Image data were not transcribed |
| Time-resolved photoluminescence lifetime fit (toluene, λex = 405 nm, λem = 499 nm) | CHI: 1.21; τav: 0.32 ns; τ1: 0.02 ns; τ2: 0.39 ns; A1: 1505.72; A2: 314.41 |
| Time-resolved photoluminescence lifetime fit (THF, λex = 405 nm, λem = 500 nm) | CHI: 1.30; τav: 0.35 ns; τ1: 0.05 ns; τ2: 0.41 ns; A1: 486.07; A2: 331.07 |
| Time-resolved photoluminescence lifetime fit (DCM, λex = 405 nm, λem = 500 nm) | CHI: 1.33; τav: 0.32 ns; τ1: 0.05 ns; τ2: 0.37 ns; A1: 428.15; A2: 325.35 |
| Time-resolved photoluminescence lifetime fit (MeCN, λex = 405 nm, λem = 499 nm) | CHI: 1.16; τav: 0.30 ns; τ1: 0.05 ns; τ2: 0.35 ns; A1: 450.20; A2: 337.47 |
| Time-resolved photoluminescence decay curves (various solvents) | Image data were not transcribed |
| CD, absorption and gabs spectra (toluene, c = 10⁻⁵ M); CPL, DC and glum spectra (toluene, c = 10⁻⁶ M, excited at 330 nm) | |glum|: 1.0 × 10⁻³; image data were not transcribed |
| Concentration-dependent UV–vis absorption and CD spectra (toluene, 25 °C, 1 cm path length) | Maximum absorbance: 0.2, 0.5, 1.2; image data were not transcribed |
| Single-crystal XRD, CCDC number | 2549006 |
| Single-crystal XRD, empirical formula | C₂₇H₁₆B₄N₆O₃F₆Cl₂I₂ |
| Single-crystal XRD, formula weight | 954.40 |
| Single-crystal XRD (150 K, λ = 1.54184 Å), crystal system and space group | monoclinic; Ia |
| Single-crystal XRD, unit cell | a = 9.71582(6) Å, α = 90°; b = 23.21701(16) Å, β = 98.7770(6)°; c = 14.44605(9) Å, γ = 90°; V = 3220.47(4) ų; Z = 4 |
| Single-crystal XRD, calculated density | 1.968 g cm⁻³ |
| Single-crystal XRD, absorption coefficient and F(000) | 17.565 mm⁻¹; 1832.0 |
| Single-crystal XRD, data collection | θ = 3.634 to 77.423°; 30129 reflections collected; 5580 independent reflections [Rint = 0.0411; Rsigma = 0.0235] |
| Single-crystal XRD, refinement | Data/restraints/parameters: 5580/2/451; goodness-of-fit on F²: 1.035 |
| Single-crystal XRD, R indices | R1 [I > 2σ(I)] = 0.0418; wR2 (all data) = 0.1005 |
| Single-crystal XRD, largest difference peak and hole | 1.24/−0.99 e Å⁻³ |
| Single-crystal XRD, dihedral angles | C–C–C–C: 11.18(11)°; C–C–C–O: −15.53(16)° and −20.26(16)° |
| Single-crystal XRD molecular-structure image | Image data were not transcribed |
| ¹H NMR (400 MHz, CDCl₃) | δ = 8.27–8.26 (dd, J = 4.0 Hz, 1.1 Hz, 2H), 8.20–8.18 (d, 9.3 Hz, 2H), 7.70 (s, 2H), 7.69–7.68 (dd, J = 5.0 Hz, 1.1 Hz, 2H), 7.32–7.30 (d, J = 9.0 Hz, 2H), 6.86–6.84 (dd, J = 4.9 Hz, 4.0 Hz, 2H) |
|---|---|
| ¹⁹F NMR (377 MHz, CDCl₃) | δ = –131.78 (s, 2F), –146.31 (s, 4F) |
| ¹¹B NMR (128 MHz, CDCl₃) | δ = 3.29 |
| NMR spectra | Image data were not transcribed |
| HRMS (FAB, positive) | m/z calcd. for C₂₂H₁₂B₄F₆N₆O₃S₂ [M]⁺ 630.0689; found: 630.0704 |
| Elemental analysis | Calcd (%) for [1e] (C₂₂H₁₂B₄F₆N₆O₃S₂·2.1 H₂O·1.3 CH₂Cl₂) (%): C, 35.97; H, 2.44; N, 10.80. Found: C, 36.28; H, 2.78; N, 10.48 |
| Melting point | > 300 °C |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 331, 430, 455 nm; λem: 510 nm; ΦPL: 23 %; τav: 1.89 ns; kr: 1.22 × 10⁸ s⁻¹; knr: 4.07 × 10⁸ s⁻¹; image data were not transcribed |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene, c = 10⁻⁶ M) | λabsmax: 331, 430 nm; λemmax, excited at λabsmax: 510 nm; ΦPL, excited at 330 nm: 0.23; τav: 1.83 ns; Stokes shift: 3650 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (THF, c = 10⁻⁶ M) | λabsmax: 327, 426 nm; λemmax, excited at λabsmax: 514 nm; ΦPL, excited at 330 nm: 0.06; τav: 1.02 ns; Stokes shift: 4020 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (DCM, c = 10⁻⁶ M) | λabsmax: 327, 427 nm; λemmax, excited at λabsmax: 513 nm; ΦPL, excited at 330 nm: 0.14; τav: 1.56 ns; Stokes shift: 3930 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (MeCN, c = 10⁻⁶ M) | λabsmax: 326, 421 nm; λemmax, excited at λabsmax: 519 nm; ΦPL, excited at 330 nm: 0.05; τav: 0.81 ns; Stokes shift: 4490 cm⁻¹ |
| UV–vis absorption, emission and excitation spectra (various solvents, c = 10⁻⁶ M) | Image data were not transcribed |
| Time-resolved photoluminescence lifetime fit (toluene, λex = 405 nm, λem = 510 nm) | CHI: 1.20; τav: 1.83 ns; τ1: 0.30 ns; τ2: 1.82 ns; A1: −16.40; A2: 393.01 |
| Time-resolved photoluminescence lifetime fit (THF, λex = 405 nm, λem = 514 nm) | CHI: 1.11; τav: 1.02 ns; τ1: 0.03 ns; τ2: 1.00 ns; A1: −315.20; A2: 480.39 |
| Time-resolved photoluminescence lifetime fit (DCM, λex = 405 nm, λem = 513 nm) | CHI: 1.12; τav: 1.56 ns; τ1: 0.09 ns; τ2: 1.47 ns; A1: −481.05; A2: 447.13 |
| Time-resolved photoluminescence lifetime fit (MeCN, λex = 405 nm, λem = 519 nm) | CHI: 1.01; τav: 0.81 ns; τ1: 0.03 ns; τ2: 0.75 ns; A1: −1050.72; A2: 586.59 |
| Time-resolved photoluminescence decay curves (various solvents) | Image data were not transcribed |
| CD, absorption and gabs spectra (toluene, c = 10⁻⁵ M); CPL, DC and glum spectra (toluene, c = 10⁻⁶ M, excited at 310 nm) | Image data were not transcribed |
| Concentration-dependent UV–vis absorption and CD spectra (toluene, 25 °C, 1 cm path length) | Maximum absorbance: 0.2, 0.5, 1.2; image data were not transcribed |
| Single-crystal XRD, CCDC number | 2549007 |
| Single-crystal XRD, empirical formula | C₂₄H₁₄B₄Cl₆F₆N₆O₃S₂ |
| Single-crystal XRD, formula weight | 868.47 |
| Single-crystal XRD (123 K, λ = 0.71073 Å), crystal system and space group | triclinic; P-1 |
| Single-crystal XRD, unit cell | a = 9.2692(2) Å, α = 70.624(2)°; b = 12.7313(3) Å, β = 77.120(2)°; c = 15.5925(4) Å, γ = 74.660(2)°; V = 1655.42(7) ų; Z = 2 |
| Single-crystal XRD, calculated density | 1.690 g cm⁻³ |
| Single-crystal XRD, absorption coefficient and F(000) | 0.303 mm⁻¹; 864.0 |
| Single-crystal XRD, data collection | θ = 2.304 to 25.347°; 31477 reflections collected; 6059 independent reflections [Rint = 0.0272; Rsigma = 0.0186] |
| Single-crystal XRD, refinement | Data/restraints/parameters: 6059/13/482; goodness-of-fit on F²: 1.053 |
| Single-crystal XRD, R indices | R1 [I > 2σ(I)] = 0.0290; wR2 (all data) = 0.0772 |
| Single-crystal XRD, largest difference peak and hole | 0.68/−0.65 e Å⁻³ |
| Single-crystal XRD (293 K), dihedral angles | C–C–C–C: 11.01(2)°; S–C–C–O: 4.67(2)° and 6.59(2)° |
| Single-crystal XRD molecular-structure image (293 K) | Image data were not transcribed |
| ¹H NMR (400 MHz, CD₂Cl₂) | δ = 8.93–8.90 (d, J = 9.3 Hz, 2H), 8.44–8.42 (m, 2H), 8.38–8.35 (d, J = 9.5 Hz, 2H), 8.34–8.32 (d, J = 9.3 Hz, 2H), 8.31–8.29 (d, J = 8.3 Hz, 2H), 8.23–8.16 (m, 4H), 7.81 (s, 2H), 7.43–7.39 (d, J = 9.1 Hz, 2H), 7.25–7.23 (d, J = 9.0 Hz, 2H), 6.82–6.80 (d, J = 8.3 Hz, 2H), 6.45–6.42 (d, J = 9.0 Hz, 2H) |
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| ¹⁹F NMR (377 MHz, CD₂Cl₂) | δ = –125.63 (s, 2F), (–144.30)–(–143.73) (d, 2F), (–145.01)–(–145.50) (d, 2F) |
| NMR spectra | Image captions specify CDCl₃; image data were not transcribed |
| HRMS (FAB, positive) | m/z calcd. for C₄₆H₂₆B₄F₆N₆O₃ [M]⁺ 866.2184; found: 866.2214 |
| Elemental analysis | Calcd (%) for [1f] (C₄₆H₂₆B₄F₆N₆O₃·1.8 CH₂Cl₂·0.7 hexane) (%): C, 57.77; H, 3.67; N, 7.77. Found: C, 57.93; H, 3.45; N, 7.55 |
| Melting point | > 300 °C |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 373 nm; λem: 513, 547 nm; ΦPL: 29 %; τav: 1.86 ns, excited at 365 and 405 nm; kr: 1.56 × 10⁸ s⁻¹; knr: 3.82 × 10⁸ s⁻¹; image data were not transcribed |
| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene, c = 10⁻⁶ M) | λabsmax: 373 nm; λemmax, excited at λabsmax: 513, 547 nm; ΦPL, excited at 330 nm: 0.29; τav: 1.87 ns; Stokes shift: 7320, 8530 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (THF, c = 10⁻⁶ M) | λabsmax: 371 nm; λemmax, excited at λabsmax: 544 nm; ΦPL, excited at 330 nm: 0.09; τav: 1.17 ns; Stokes shift: 8570 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (DCM, c = 10⁻⁶ M) | λabsmax: 372 nm; λemmax, excited at λabsmax: 548 nm; ΦPL, excited at 330 nm: 0.14; τav: 1.32 ns; Stokes shift: 8630 cm⁻¹ |
| UV–vis absorption, photoluminescence and fluorescence lifetime (MeCN, c = 10⁻⁶ M) | λabsmax: 367 nm; λemmax, excited at λabsmax: 556 nm; ΦPL, excited at 330 nm: 0.03; τav: 0.40 ns; Stokes shift: 9260 cm⁻¹ |
| UV–vis absorption, emission and excitation spectra (various solvents, c = 10⁻⁶ M) | Image data were not transcribed |
| Time-resolved photoluminescence lifetime fit (toluene, λex = 365 nm, λem = 547 nm) | CHI: 1.26; τav: 1.87 ns; τ1: 0.41 ns; τ2: 1.84 ns; A1: −36.22; A2: 382.04 |
| Time-resolved photoluminescence lifetime fit (THF, λex = 365 nm, λem = 544 nm) | CHI: 1.22; τav: 1.17 ns; τ1: 0.02 ns; τ2: 1.20 ns; A1: 596.91; A2: 409.41 |
| Time-resolved photoluminescence lifetime fit (DCM, λex = 365 nm, λem = 548 nm) | CHI: 1.29; τav: 1.32 ns; τ1: 0.19 ns; τ2: 1.29 ns; A1: −75.80; A2: 428.53 |
| Time-resolved photoluminescence lifetime fit (MeCN, λex = 365 nm, λem = 556 nm) | CHI: 1.18; τav: 0.40 ns; τ1: 0.19 ns; τ2: 1.83 ns; A1: 409.46; A2: 6.36 |
| Time-resolved photoluminescence decay curves (various solvents) | Image data were not transcribed |
| CD, absorption and gabs spectra (toluene, c = 10⁻⁵ M); CPL, DC and glum spectra (toluene, c = 10⁻⁶ M, excited at 310 nm) | Image data were not transcribed |
| Concentration-dependent UV–vis absorption and CD spectra (toluene, 25 °C, 1 cm path length) | Maximum absorbance: 0.2, 0.5, 1.2; image data were not transcribed |
| Single-crystal XRD, CCDC number | 2549008 |
| Single-crystal XRD, empirical formula | C₄₇H₂₆B₄Cl₂F₆N₆O₃ |
| Single-crystal XRD, formula weight | 950.88 |
| Single-crystal XRD (123 K, λ = 0.71073 Å), crystal system and space group | monoclinic; P2₁/n |
| Single-crystal XRD, unit cell | a = 7.7093(3) Å, α = 90°; b = 34.6378(13) Å, β = 95.105(4)°; c = 16.2144(6) Å, γ = 90°; V = 4312.6(3) ų; Z = 4 |
| Single-crystal XRD, calculated density | 1.465 g cm⁻³ |
| Single-crystal XRD, absorption coefficient and F(000) | 0.228 mm⁻¹; 1928.0 |
| Single-crystal XRD, data collection | θ = 2.168 to 25.35°; 40216 reflections collected; 7895 independent reflections [Rint = 0.0661; Rsigma = 0.0531] |
| Single-crystal XRD, refinement | Data/restraints/parameters: 7895/13/622; goodness-of-fit on F²: 1.047 |
| Single-crystal XRD, R indices | R1 [I > 2σ(I)] = 0.0759; wR2 (all data) = 0.2315 |
| Single-crystal XRD, largest difference peak and hole | 0.89/−1.10 e Å⁻³ |
| Single-crystal XRD, dihedral angles | C–C–C–C: 11.75(11)°; C–C–C–O: 25.65(5)° and −24.99(5)° |
| Single-crystal XRD molecular-structure image | Image data were not transcribed |
| Circular dichroism (toluene) | |gabs|: 4.3 × 10⁻³ to 6.2 × 10⁻³ |
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| UV–vis absorption, photoluminescence and fluorescence lifetime (toluene) | λabs: 334 nm; λem: 530 nm; ΦPL: 4 %; τav: 0.50 ns, excited at 340 nm; kr: 0.80 × 10⁸ s⁻¹; knr: 19.20 × 10⁸ s⁻¹; image data were not transcribed |
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| Transient absorption (degassed toluene, 293 K, excited at 400 nm) | Global analysis yielded five time constants; τ₄ = 0.52 ns, assigned to S₁ depopulation; τav = 0.50 ns; the long-lived τ₅ component, assigned to a T₁ state, remained constant within the observed time window; image data were not transcribed |