| NMR reporting reference | Chemical shifts (δ) are reported in parts per million (ppm) and were referenced to the residual non-deuterated solvent of the deuterated solvent used; CDCl₃: δ ¹H = 7.26 (CHCl₃) and ¹³C = 77.16 (CDCl₃); (CD₃)₂SO: ¹H = 2.50 ((CD₃)(CD₂H)SO) and ¹³C = 39.52 ((CD₃)₂SO) |
|---|---|
| ¹H NMR (700 MHz, DMSO-d₆) | δ 8.34 (d, J = 8.4 Hz, 2H, H-7), 7.98 (dd, J = 8.5, 1.1 Hz, 2H, H-12), 7.94 (dd, J = 8.2, 1.4 Hz, 2H, H-9), 7.76 – 7.71 (m, 4H, H-6, H-11), 7.57 (ddd, J = 8.1, 6.8, 1.2 Hz, 2H, H-10), 4.03 (s, 4H, H-4), 3.43 (d, J = 2.4 Hz, 2H, H-3), 3.28 (t, J = 2.3 Hz, 1H, H-1) |
| ¹³C NMR {¹H} (176 MHz, DMSO-d₆) | δ 159.49 (C-5), 146.99 (C-13), 136.55 (C-7), 129.49 (C-11), 128.59 (C-12), 127.79 (C-9), 127.04 (C-8), 126.23 (C-10), 120.95 (C-6), 78.68 (C-2), 76.38 (C-1), 59.50 (C-4), 42.31 (C-3) |
| HRMS (ESI+) | (C₂₃H₂₀N₃)⁺ m/z (calculated) 338.1652, (found) 338.1661, mass difference 2.9 ppm |
| HRMS (ESI+), service report | (C₂₃H₂₀N₃) measured m/z 338.1661, calculated m/z 338.1652, error -2.6 ppm (-0.9 mDa), MSigma 1.5, mean error -2.9 ppm; (C₂₃H₁₉N₃Na) measured m/z 360.1480, calculated m/z 360.1471, error -2.4 ppm (-0.9 mDa), MSigma 1.5, mean error -2.8 ppm |
| ATIR | ṽ (cm⁻¹) 3158, 3056, 1600, 1564, 1501, 1444, 1310, 952, 829, 815, 763 (s), 744 (s), 620, 475 |
| FT-IR peak assignment | 2099 cm⁻¹ peak is MeCN of crystallization |
| Experimental and calculated lifetime data (solid state; EPL-375 excitation; emission monitored at 440 nm through a 420 nm long-pass filter) | t₁ (Rel. %) 3.55 (22.5 %), t₁ (Rel. %) 12.86 (75.1 %), t₁ (Rel. %) 135.8 (2.4 %), tave (ns) 13.0 |
| Excitation (nm, solid state) | 360 |
| Emission (nm, solid state) | 444 |
| Stokes shift (cm⁻¹, solid state) | 5300 |
| Single-crystal X-ray diffraction, identification code | af25013 |
| Single-crystal X-ray diffraction, CCDC deposition number | 2579908 |
| Single-crystal X-ray diffraction, selected interatomic lengths (Å) | C22-C23 = 1.1881(16); N2-C21 = 1.4684(13); N2-C10 = 1.4715(13); N2-C20 = 1.4656(13); C9-C10 = 1.5081(14) |
| Single-crystal X-ray diffraction, selected interatomic angles (°) | C23-C22-C21 = 178.07(11); C21-N2-C20 = 111.87(8); N1-C9-C10 = 117.35(9) |
| Single-crystal X-ray diffraction, refinement qualifier | C13 and C14 are not ideally shaped, giving a checkCIF B level alert. This does not indicate an incorrect atom-type assignment |
| Empirical formula | C₂₃H₁₉N₃ |
| Formula weight | 337.41 |
| Temperature (K) | 110.0(2) |
| Crystal system | triclinic |
| Space group | P-1 |
| Cell dimensions, a, b, c (Å) | 8.4004(3), 9.7598(3), 11.9274(4) |
| Cell dimensions, α, β, γ (°) | 71.932(3), 76.799(3), 85.522(2) |
| Volume (ų) | 905.07(6) |
| Z | 2 |
| ρcalc (g/cm³) | 1.238 |
| μ (mm⁻¹) | 0.574 |
| F(000) | 356.0 |
| Crystal size (mm³) | 0.776 × 0.313 × 0.216 |
| Radiation | Cu Kα (λ = 1.54184) |
| 2Θ range for data collection (°) | 7.984 to 136.496 |
| Index ranges | -9 ≤ h ≤ 10, -11 ≤ k ≤ 11, -14 ≤ l ≤ 14 |
| Reflections collected | 16634 |
| Independent reflections | 3304 [Rint = 0.0323, Rsigma = 0.0209] |
| Data/restraints/parameters | 3304/0/236 |
| Goodness-of-fit on F² | 1.044 |
| Final R indexes [I≥2σ (I)] | R1 = 0.0342, wR2 = 0.0881 |
| Final R indexes [all data] | R1 = 0.0358, wR2 = 0.0894 |
| Largest diff. peak/hole (e Å⁻³) | 0.19/-0.19 |
David R. Husbands, Gustavo Clauss, Lukas Geciauskas, Robin E. Kroon, Mmabatho L. Ledibane, Orbett Alexander, Angelo Frei. “Synthesis, physical, chemical and biological properties of a M(CO)₃ (M = Cr, Mo, W, Mn, Re) matched quintet.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007450/v2
| NMR reporting reference | Chemical shifts (δ) are reported in parts per million (ppm) and were referenced to the residual non-deuterated solvent of the deuterated solvent used; CDCl₃: δ ¹H = 7.26 (CHCl₃) and ¹³C = 77.16 (CDCl₃); (CD₃)₂SO: ¹H = 2.50 ((CD₃)(CD₂H)SO) and ¹³C = 39.52 ((CD₃)₂SO) |
|---|---|
| ¹H NMR (700 MHz, DMSO-d₆) | δ 9.23 (d, J = 8.7 Hz, 2H, H-12), 8.30 (d, J = 8.4 Hz, 2H, H-7), 7.93 (d, J = 8.0 Hz, 2H, H-9), 7.78 (t, J = 7.8 Hz, 2H, H-11), 7.59 (t, J = 7.6 Hz, 2H, H-10), 7.46 (d, J = 8.4 Hz, 2H, H-6), 4.74 (d, J = 17.1 Hz, 2H, H-4), 4.44 (s, 2H, H-3), 4.40 (d, J = 17.1 Hz, 2H, H-4), 3.63 (d, J = 2.4 Hz, 1H, H-1) |
| ¹³C NMR {¹H} (176 MHz, DMSO-d₆) | δ 234.01 (C≡O), 231.91 (C≡O), 161.95 (C-5), 147.76 (C-13), 137.78 (C-7), 130.44 (C-11), 129.30 (C-12), 128.55 (C-9), 127.67 (C-8), 126.78 (C-10), 119.05 (C-6), 78.06 (C-1), 77.50 (C-2), 65.54 (C-4), 52.98 (C-3) |
| H-4 ¹H NMR shift (ppm) | 4.57 |
| H-4 J coupling (Hz) | 17.16 |
| ν₀Δ (ppm; calculated from four H-4 frequencies) | 0.339 |
| ¹H NMR free-ligand impurity | 9 % (integral of peak at 4.03 ppm) |
| HRMS (LIFDI) | (C₂₆H₁₉N₃O₃Cr)⁺˙ m/z (calculated) 473.08260, (found) 473.08167, mass difference 1.97 ppm |
| LIFDI mass spectrum | peak at 417 is [complex – 2 × CO] |
| ATIR | ṽ (cm⁻¹) 1886 (vs, C≡O), 1754 (vs, C≡O) |
| λmax (UV–Vis, DMSO, nominal 33 µM, 10.00 mm path length) / nm | 485.8, 368, 295.8 |
| Emission λmax (DMSO) / nm | 440 |
| Experimental and calculated lifetime data (solid state; EPL-375 excitation; emission monitored at 440 nm through a 420 nm long-pass filter) | t₁ (Rel. %) 4.03 (23.6 %), t₁ (Rel. %) 12.82 (74.2 %), t₁ (Rel. %) 131.9 (2.2 %), tave (ns) 13.3 |
| Excitation (nm, solid state) | 358 |
| Emission (nm, solid state) | 440 |
| Stokes shift (cm⁻¹, solid state) | 5200 |
| NMR reporting reference | Chemical shifts (δ) are reported in parts per million (ppm) and were referenced to the residual non-deuterated solvent of the deuterated solvent used; CDCl₃: δ ¹H = 7.26 (CHCl₃) and ¹³C = 77.16 (CDCl₃); (CD₃)₂SO: ¹H = 2.50 ((CD₃)(CD₂H)SO) and ¹³C = 39.52 ((CD₃)₂SO) |
|---|---|
| ¹H NMR (700 MHz, DMSO-d₆) | δ 9.08 (dd, J = 8.7, 1.1 Hz, 2H, H-12), 8.32 – 8.28 (m, 2H, H-7), 7.86 (dd, J = 8.1, 1.5 Hz, 2H, H-9), 7.77 (ddd, J = 8.6, 6.9, 1.5 Hz, 2H, H-11), 7.54 (ddd, J = 8.0, 6.9, 1.1 Hz, 2H, H-10), 7.51 (d, J = 8.5 Hz, 2H, H-6), 4.73 (d, J = 16.6 Hz, 2H, H-4), 4.54 (d, J = 16.7 Hz, 2H, H-4), 4.39 (d, J = 2.4 Hz, 2H, H-3), 3.65 (t, J = 2.4 Hz, 1H, H-1) |
| ¹³C NMR {¹H} (176 MHz, DMSO-d₆) | δ 228.80 (C≡O), 228.25 (C≡O), 161.59 (C-5), 146.89 (C-13), 138.23 (C-7), 130.56 (C-11), 129.87 (C-12), 128.25 (C-9), 127.19 (C-10), 127.00 (C-8), 119.99 (C-6), 78.54 (C-1), 77.17 (C-2), 65.52 (C-4), 53.67 (C-3) |
| H-4 ¹H NMR shift (ppm) | 4.64 |
| H-4 J coupling (Hz) | 16.62 |
| ν₀Δ (ppm; calculated from four H-4 frequencies) | 0.186 |
| ¹H NMR free-ligand impurity | 3 % (integral of peak at 4.03 ppm) |
| HRMS (LIFDI) | (C₂₆H₁₉N₃O₃Mo)⁺˙ m/z (calculated) 519.04750, (found) 519.04952, mass difference 3.88 ppm |
| ATIR | ṽ (cm⁻¹) 1888 (vs, C≡O), 1748 (vs, br, C≡O) |
| λmax (UV–Vis, DMSO, nominal 33 µM, 10.00 mm path length) / nm | 457, 298 |
| UV–Vis absorption band at 368 nm | absent |
| Emission λmax (DMSO) / nm | 442 |
| Experimental and calculated lifetime data (solid state; EPL-375 excitation; emission monitored at 440 nm through a 420 nm long-pass filter) | t₁ (Rel. %) 3.37 (21.3 %), t₁ (Rel. %) 12.84 (76.5 %), t₁ (Rel. %) 147.6 (2.2 %), tave (ns) 13.8 |
| Excitation (nm, solid state) | 360 |
| Emission (nm, solid state) | 442 |
| Stokes shift (cm⁻¹, solid state) | 5200 |
| Single-crystal X-ray diffraction, identification code | af25014 |
| Single-crystal X-ray diffraction, CCDC deposition number | 2579905 |
| Single-crystal X-ray diffraction, selected interatomic lengths (Å) | C1-O1 = 1.172(4); C2-O2 = 1.172(4); C3-O3 = 1.176(4); Mo1-C1 = 1.938(3); Mo1-C2 = 1.938(3); Mo1-C3 = 1.933(3); Mo1-N1 = 2.292(2); Mo1-N2 = 2.305(2); Mo1-N3 = 2.307(2) |
| Single-crystal X-ray diffraction, selected interatomic angles (°) | O1-C1-Mo1 = 175.4(2); O2-C2-Mo1 = 178.2(2); O3-C3-Mo1 = 173.6(2); C1-Mo1-C2 = 86.54(12); C2-Mo1-C3 = 89.27(12); C3-Mo1-C1 = 79.15(12); N1-Mo1-N2 = 71.43(8); N2-Mo1-N3 = 76.01(8); N3-Mo1-N1 = 81.76(8) |
| Empirical formula | C₂₆H₁₉N₃O₃Mo |
| Formula weight | 517.38 |
| Temperature (K) | 109.97(14) |
| Crystal system | triclinic |
| Space group | P-1 |
| Cell dimensions, a, b, c (Å) | 7.5252(2), 9.0176(2), 16.0214(4) |
| Cell dimensions, α, β, γ (°) | 96.178(2), 98.891(2), 93.750(2) |
| Volume (ų) | 1064.17(5) |
| Z | 2 |
| ρcalc (g/cm³) | 1.615 |
| μ (mm⁻¹) | 5.334 |
| F(000) | 524.0 |
| Crystal size (mm³) | 0.101 × 0.047 × 0.037 |
| Radiation | Cu Kα (λ = 1.54184) |
| 2Θ range for data collection (°) | 5.624 to 136.49 |
| Index ranges | -9 ≤ h ≤ 9, -10 ≤ k ≤ 10, -19 ≤ l ≤ 19 |
| Reflections collected | 19425 |
| Independent reflections | 3893 [Rint = 0.0481, Rsigma = 0.0298] |
| Data/restraints/parameters | 3893/0/302 |
| Goodness-of-fit on F² | 1.091 |
| Final R indexes [I≥2σ (I)] | R1 = 0.0324, wR2 = 0.0866 |
| Final R indexes [all data] | R1 = 0.0340, wR2 = 0.0878 |
| Largest diff. peak/hole (e Å⁻³) | 1.48/-1.38 |
| NMR reporting reference | Chemical shifts (δ) are reported in parts per million (ppm) and were referenced to the residual non-deuterated solvent of the deuterated solvent used; CDCl₃: δ ¹H = 7.26 (CHCl₃) and ¹³C = 77.16 (CDCl₃); (CD₃)₂SO: ¹H = 2.50 ((CD₃)(CD₂H)SO) and ¹³C = 39.52 ((CD₃)₂SO) |
|---|---|
| ¹H NMR (700 MHz, DMSO) | δ 9.10 (dd, J = 8.6, 1.0 Hz, 2H, H-12), 8.35 – 8.32 (m, 2H, H-7), 7.87 (dd, J = 8.0, 1.5 Hz, 2H, H-9), 7.75 (ddd, J = 8.7, 6.9, 1.6 Hz, 2H, H-11), 7.55 – 7.53 (m, 4H, H-10, H-6), 4.81 – 4.74 (m, 4H, H-4), 4.47 (d, J = 2.4 Hz, 2H, H-3), 3.71 (t, J = 2.4 Hz, 1H, H-1) |
| ¹³C NMR {¹H} (176 MHz, DMSO) | δ 224.37 (C≡O), 223.14 (C≡O), 162.66 (C-5), 146.79 (C-13), 138.25 (C-7), 130.80 (C-11), 130.62 (C-12), 128.36 (C-9), 127.25 (C-8), 127.17 (C-10), 119.98 (C-6), 78.86 (C-1), 77.51 (C-2), 66.74 (C-4), 55.16 (C-3) |
| H-4 ¹H NMR shift (ppm) | 4.78 |
| H-4 J coupling (Hz) | 16.87 |
| ν₀Δ (ppm; calculated from four H-4 frequencies) | 0.016 |
| ¹H NMR free-ligand impurity | 6 % (integral of peak at 4.03 ppm) |
| ¹H NMR residual acetone | present at 2.08 ppm |
| ¹³C NMR residual acetone | peaks are at 206.53 and 30.70 ppm |
| HRMS (LIFDI) | (C₂₆H₁₉N₃O₃W)⁺˙ m/z (calculated) 605.09303, (found) 605.09267, mass difference 0.59 ppm |
| LIFDI mass spectrum | peak at 567 is [M – 2 × CO, +H₂O] |
| ATIR | ṽ (cm⁻¹) 1879 (vs, C≡O), 1743 (vs, C≡O) |
| λmax (UV–Vis, DMSO, nominal 33 µM, 10.00 mm path length) / nm | 478.2, 315.6, 302.6, 296.6 |
| UV–Vis absorption band at 368 nm | absent |
| Emission λmax (DMSO) / nm | 434 |
| Experimental and calculated lifetime data (solid state; EPL-375 excitation; emission monitored at 440 nm through a 420 nm long-pass filter) | t₁ (Rel. %) 3.66 (27.1 %), t₁ (Rel. %) 12.88 (70.8 %), t₁ (Rel. %) 129.13 (2.1 %), tave (ns) 12.8 |
| Excitation (nm, solid state) | 341 |
| Emission (nm, solid state) | 434 |
| Stokes shift (cm⁻¹, solid state) | 6300 |
| NMR reporting reference | Chemical shifts (δ) are reported in parts per million (ppm) and were referenced to the residual non-deuterated solvent of the deuterated solvent used; CDCl₃: δ ¹H = 7.26 (CHCl₃) and ¹³C = 77.16 (CDCl₃); (CD₃)₂SO: ¹H = 2.50 ((CD₃)(CD₂H)SO) and ¹³C = 39.52 ((CD₃)₂SO) |
|---|---|
| ¹H NMR (700 MHz, DMSO) | δ 8.62 (d, J = 8.4 Hz, 2H, H-7), 8.35 (d, J = 8.7 Hz, 2H, H-12), 8.16 (dd, J = 8.2, 1.5 Hz, 2H, H-9), 7.92 (ddd, J = 8.7, 7.0, 1.5 Hz, 2H, H-11), 7.75 (t, J = 7.5 Hz, 2H, H-10), 7.67 (d, J = 8.4 Hz, 2H, H-6), 5.11 (d, J = 18.2 Hz, 2H, H-4), 4.80 (d, J = 18.2 Hz, 2H, H-4), 4.71 (d, J = 2.4 Hz, 2H, H-3), 3.91 (d, J = 2.3 Hz, 1H, H-1) |
| ¹³C NMR {¹H} (176 MHz, DMSO) | δ 219.65 (C≡O), 218.41 (C≡O), 164.71 (C-5), 147.04 (C-13), 140.51 (C-7), 132.29 (C-11), 129.95 (C-9), 128.55 (C-8), 127.70 (C-10), 126.05 (C-12), 119.72 (C-6), 80.76 (C-1), 77.80 (C-2), 68.39 (C-4), 53.92 (C-3) |
| ¹⁹F NMR (659 MHz, DMSO) | δ -77.74 (s) |
| H-4 ¹H NMR shift (ppm) | 4.95 |
| H-4 J coupling (Hz) | 18.20 |
| ν₀Δ (ppm; calculated from four H-4 frequencies) | 0.308 |
| HRMS (ESI+) | (C₂₆H₁₉MnN₃O₃)⁺ m/z (calculated) 476.0801, (found) 476.0795, mass difference 1.9 ppm |
| LCMS (compound-characterization record; ESI+; 7 min method; H₂O:MeCN, 0.1 % formic acid) | 2.57 min, m/z 313.11 |
| LCMS (LC-MS data record; 7 min method) | 3.43 min, m/z 476.03 |
| LCMS injection peak | The sample was prepared from a 10 mM stock in DMSO, leading to an injection peak at 0.96 min |
| LCMS 7 min method gradient (time / min, flow / mL min⁻¹, MeCN) | 0.0, 0.300, 10.0 %; 4.0, 0.300, 90.0 %; 6.3, 0.300, 90.0 %; 6.4, 0.300, 10.0 %; 7.0, 0.300, 10.0 % |
| ATIR | ṽ (cm⁻¹) 2030 (vs, C≡O), 1941 (vs, C≡O), 1923 (vs, C≡O) |
| λmax (UV–Vis, DMSO, nominal 33 µM, 10.00 mm path length) / nm | 361.8, 321.2, 310 |
| Emission λmax (DMSO) / nm | 436 |
| Fluorescence quantum yield (solid state) | 11 % |
| Experimental and calculated lifetime data (solid state; EPL-375 excitation; emission monitored at 440 nm through a 420 nm long-pass filter) | t₁ (Rel. %) 3.13 (48.9 %), t₁ (Rel. %) 12.97 (48.6 %), t₁ (Rel. %) 137.0 (2.5 %), tave (ns) 11.3 |
| Excitation (nm, solid state) | 355 |
| Emission (nm, solid state) | 436 |
| Stokes shift (cm⁻¹, solid state) | 5200 |
| Single-crystal X-ray diffraction, identification code | af25015 |
| Single-crystal X-ray diffraction, CCDC deposition number | 2579909 |
| Single-crystal X-ray diffraction, selected interatomic lengths (Å) | C1-O1 = 1.144(2); C2-O2 = 1.144(2); C3-O3 = 1.153(2); Mn1-C1 = 1.8224(19); Mn1-C2 = 1.8097(18); Mn1-C3 = 1.8086(18); Mn1-N1 = 2.1145(14); Mn1-N2 = 2.0952(14); Mn1-N3 = 2.1072(15) |
| Single-crystal X-ray diffraction, selected interatomic angles (°) | O1-C1-Mn1 = 174.17(15); O2-C2-Mn1 = 173.89(16); O3-C3-Mn1 = 171.48(16); C1-Mn1-C2 = 87.20(8); C2-Mn1-C3 = 81.65(8); C3-Mn1-C1 = 87.40(8); N1-Mn1-N2 = 81.24(6); N2-Mn1-N3 = 75.96(6); N3-Mn1-N1 = 90.97(5) |
| Empirical formula | C₂₇H₁₉N₃O₆F₃SMn |
| Formula weight | 625.45 |
| Temperature (K) | 109.98(11) |
| Crystal system | monoclinic |
| Space group | P2₁/c |
| Cell dimensions, a, b, c (Å) | 12.79020(10), 15.19890(10), 14.14890(10) |
| Cell dimensions, α, β, γ (°) | 90, 106.0330(10), 90 |
| Volume (ų) | 2643.52(4) |
| Z | 4 |
| ρcalc (g/cm³) | 1.572 |
| μ (mm⁻¹) | 5.424 |
| F(000) | 1272.0 |
| Crystal size (mm³) | 0.187 × 0.142 × 0.115 |
| Radiation | Cu Kα (λ = 1.54184) |
| 2Θ range for data collection (°) | 7.192 to 136.468 |
| Index ranges | -10 ≤ h ≤ 15, -16 ≤ k ≤ 18, -17 ≤ l ≤ 17 |
| Reflections collected | 24693 |
| Independent reflections | 4838 [Rint = 0.0276, Rsigma = 0.0208] |
| Data/restraints/parameters | 4838/0/371 |
| Goodness-of-fit on F² | 1.056 |
| Final R indexes [I≥2σ (I)] | R1 = 0.0305, wR2 = 0.0804 |
| Final R indexes [all data] | R1 = 0.0313, wR2 = 0.0809 |
| Largest diff. peak/hole (e Å⁻³) | 0.54/-0.57 |
| NMR reporting reference | Chemical shifts (δ) are reported in parts per million (ppm) and were referenced to the residual non-deuterated solvent of the deuterated solvent used; CDCl₃: δ ¹H = 7.26 (CHCl₃) and ¹³C = 77.16 (CDCl₃); (CD₃)₂SO: ¹H = 2.50 ((CD₃)(CD₂H)SO) and ¹³C = 39.52 ((CD₃)₂SO) |
|---|---|
| ¹H NMR (700 MHz, DMSO-d₆) | δ 8.71 (d, J = 8.4 Hz, 2H, H-7), 8.39 (d, J = 8.8 Hz, 2H, H-12), 8.16 (dd, J = 8.2, 1.5 Hz, 2H, H-9), 7.98 (ddd, J = 8.7, 7.0, 1.6 Hz, 2H, H-11), 7.79 – 7.74 (m, 4H, H-6, H-10), 5.23 (d, J = 18.0 Hz, 2H, H-4), 5.17 (d, J = 18.0 Hz, 2H, H-4), 4.77 (d, J = 2.5 Hz, 2H, H-3), 3.89 (t, J = 2.4 Hz, 1H, H-1) |
| ¹³C NMR {¹H} (176 MHz, DMSO-d₆) | δ 196.21 (C≡O), 193.96 (C≡O), 165.55 (C-5), 146.06 (C-13), 141.40 (C-7), 132.96 (C-11), 129.86 (C-9), 128.10 (C-10), 127.59 (C-12), 120.37 (C-6), 80.99 (C-1), 77.82 (C-2), 68.84 (C-4), 55.56 (C-3) |
| ¹³C NMR reporting note | No peak for C-8 was observed in the carbon spectrum in DMSO-d₆. In a separate NMR in DCM-d₂ of the same sample, overlapping peaks were observed at 128.99 and 128.98 ppm. As the peak in the DMSO-d₆ spectrum at 128.10 ppm (C-10) is more intense that the surrounding peak, it is assumed that this peak overlaps with the C-8 peak |
| ¹⁹F NMR (659 MHz, DMSO-d₆) | δ -77.75 |
| H-4 ¹H NMR shift (ppm) | 5.20 |
| H-4 J coupling (Hz) | 18.00 |
| ν₀Δ (ppm; calculated from four H-4 frequencies) | 0.059 |
| HRMS (ESI+) | (C₂₆H₁₉N₃O₃Re)⁺ m/z (calculated) 608.0978, (found) 608.0963, mass difference 2.3 ppm |
| LCMS (compound-characterization record; ESI+; 7 min method; H₂O:MeCN, 0.1 % formic acid) | 2.57 min, m/z 313.11 |
| LCMS (LC-MS data record; 7 min method) | 3.44 min, m/z 608.17 |
| LCMS injection peak | The sample was prepared from a 10 mM stock in DMSO, leading to an injection peak at 0.96 min |
| LCMS 7 min method gradient (time / min, flow / mL min⁻¹, MeCN) | 0.0, 0.300, 10.0 %; 4.0, 0.300, 90.0 %; 6.3, 0.300, 90.0 %; 6.4, 0.300, 10.0 %; 7.0, 0.300, 10.0 % |
| ATIR | ṽ (cm⁻¹) 2028 (vs, C≡O), 1925 (vs, C≡O), 1907 (vs, C≡O) |
| λmax (UV–Vis, DMSO, nominal 33 µM, 10.00 mm path length) / nm | 322, 315.8 |
| UV–Vis MLCT band | no obvious MLCT band observed |
| Emission λmax (DMSO) / nm | 436 |
| Fluorescence quantum yield (solid state) | 2.3 % |
| Experimental and calculated lifetime data (solid state; EPL-375 excitation; emission monitored at 440 nm through a 420 nm long-pass filter) | t₁ (Rel. %) 3.03 (48.7 %), t₁ (Rel. %) 12.84 (48.8 %), t₁ (Rel. %) 119.8 (2.5 %), tave (ns) 10.7 |
| Excitation (nm, solid state) | 363 |
| Emission (nm, solid state) | 436 |
| Stokes shift (cm⁻¹, solid state) | 4600 |
| Single-crystal X-ray diffraction, identification code | af25016 |
| Single-crystal X-ray diffraction, CCDC deposition number | 2579906 |
| Single-crystal X-ray diffraction, selected interatomic lengths (Å) | C1-O1 = 1.152(4); C2-O2 = 1.148(4); C3-O3 = 1.144(4); Re1-C1 = 1.926(3); Re1-C2 = 1.912(3); Re1-C3 = 1.926(3); Re1-N1 = 2.230(2); Re1-N2 = 2.211(2); Re1-N3 = 2.223(2) |
| Single-crystal X-ray diffraction, selected interatomic angles (°) | O1-C1-Re1 = 177.0(3); O2-C2-Re1 = 177.2(3); O3-C3-Re1 = 175.3(3); C1-Re1-C2 = 87.51(13); C2-Re1-C3 = 82.32(12); C3-Re1-C1 = 86.60(12); N1-Re1-N2 = 77.70(9); N2-Re1-N3 = 72.73(9); N3-Re1-N1 = 88.45(8) |
| Single-crystal X-ray diffraction, refinement special details | A significant Q peak next to the S on the triflate ion has been modelled as a bromide at 0.13 occupancy (triflate 0.87 occupancy) |
| Empirical formula | C₂₆.₈₇H₁₉Br₀.₁₃F₂.₆₁N₃O₅.₆₁ReS₀.₈₇ |
| Formula weight | 747.72 |
| Temperature (K) | 109.99(10) |
| Crystal system | monoclinic |
| Space group | P2₁/c |
| Cell dimensions, a, b, c (Å) | 12.82490(10), 15.28420(10), 14.18130(10) |
| Cell dimensions, α, β, γ (°) | 90, 105.3730(10), 90 |
| Volume (ų) | 2680.33(4) |
| Z | 4 |
| ρcalc (g/cm³) | 1.853 |
| μ (mm⁻¹) | 10.299 |
| F(000) | 1452.0 |
| Crystal size (mm³) | 0.134 × 0.072 × 0.036 |
| Radiation | Cu Kα (λ = 1.54184) |
| 2Θ range for data collection (°) | 7.148 to 136.502 |
| Index ranges | -15 ≤ h ≤ 15, -10 ≤ k ≤ 18, -17 ≤ l ≤ 17 |
| Reflections collected | 25172 |
| Independent reflections | 4897 [Rint = 0.0311, Rsigma = 0.0214] |
| Data/restraints/parameters | 4897/0/379 |
| Goodness-of-fit on F² | 1.052 |
| Final R indexes [I≥2σ (I)] | R1 = 0.0217, wR2 = 0.0567 |
| Final R indexes [all data] | R1 = 0.0235, wR2 = 0.0577 |
| Largest diff. peak/hole (e Å⁻³) | 0.95/-0.50 |
| HRMS (ESI+) | (C₃₃H₂₆MnN₆O₃)⁺ m/z (calculated) 609.1441, (found) 609.1444, mass difference 1.8 ppm |
|---|---|
| LCMS (compound-characterization record; ESI+; 7 min method; H₂O:MeCN, 0.1 % formic acid) | 3.98 min, m/z 609.08 (major isomer); 3.70 min, m/z 609.07 (minor isomer) |
| LCMS (LC-MS data record; 7 min method) | 3.98 min, m/z 609.13; 3.70 min, m/z 609.08 |
| LCMS 7 min method gradient (time / min, flow / mL min⁻¹, MeCN) | 0.0, 0.300, 10.0 %; 4.0, 0.300, 90.0 %; 6.3, 0.300, 90.0 %; 6.4, 0.300, 10.0 %; 7.0, 0.300, 10.0 % |
| ATIR | ṽ (cm⁻¹) 2032 (vs, C≡O), 1919 (vs, C≡O) |
| IR spectrum of the solid product | carbonyl bands at 2028 and 1925 cm⁻¹, confirming no carbonyl loss |
| ¹H NMR (700 MHz, DCM-d₂) | showing a mixture of isomers |
| Single-crystal X-ray diffraction, identification code | af26009 |
| Single-crystal X-ray diffraction, CCDC deposition number | 2579907 |
| Single-crystal X-ray diffraction, observed crystal composition | This compound crystallized as a racemate, with two enantiomers in the asymmetric unit cell |
| Single-crystal X-ray diffraction, coordination | The newly formed triazole unit can coordinate to the metal centre in place of one quinoline unit |
| Single-crystal X-ray diffraction, model qualifier | The crystals were poorly diffracting and gave rise to a high level of uncertainty in the unit cell for data collection. The final model used a smaller unit cell than that collected, so there is a large number of missing reflections. As such, there is quite a high degree of uncertainty in the model, with R1 = 0.0974, wR2 = 0.2262. This model shall not be used to obtain detailed bond lengths and angles |
| Single-crystal X-ray diffraction, residual electron density | Void of 41Å in the unit cell, corresponding to electron density of 5 electrons; likely a partially occupied site by CH₂Cl₂ or Et₂O |
| Empirical formula | C₁₈.₁₃H₁₃.₈₇F₁.₆Mn₀.₅₃N₃.₂O₃.₂S₀.₅₃ |
| Formula weight | 404.56 |
| Temperature (K) | 110.00(10) |
| Crystal system | monoclinic |
| Space group | P2₁/c |
| Cell dimensions, a, b, c (Å) | 13.1900(4), 16.3983(6), 31.1888(10) |
| Cell dimensions, α, β, γ (°) | 90, 101.759(3), 90 |
| Volume (ų) | 6604.4(4) |
| Z | 15 |
| ρcalc (g/cm³) | 1.526 |
| μ (mm⁻¹) | 4.480 |
| F(000) | 3104.0 |
| Crystal size (mm³) | 0.11 × 0.09 × 0.03 |
| Radiation | Cu Kα (λ = 1.54184) |
| 2Θ range for data collection (°) | 5.788 to 136.502 |
| Index ranges | -15 ≤ h ≤ 15, -17 ≤ k ≤ 19, -37 ≤ l ≤ 37 |
| Reflections collected | 43729 |
| Independent reflections | 11990 [Rint = 0.0726, Rsigma = 0.0615] |
| Data/restraints/parameters | 11990/0/921 |
| Goodness-of-fit on F² | 1.132 |
| Final R indexes [I≥2σ (I)] | R1 = 0.0974, wR2 = 0.2262 |
| Final R indexes [all data] | R1 = 0.1428, wR2 = 0.2465 |
| Largest diff. peak/hole (e Å⁻³) | 1.04/-0.56 |