| ¹H NMR, UV–Vis and FT-IR spectra and NMR-derived reaction-monitoring plots during 360 nm irradiation and subsequent heating at 120 °C | Image data were not transcribed |
|---|---|
| UV-LED irradiation | 365 nm, 600 mW cm⁻² |
Aoi Nakahara, Haruka Koshino, Tomoyuki Mochida. “Liquid-state photoreactions of Ru-containing ionic liquids with PF₅CN anions: ligand-dependent coordination modes and reversibility.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007793/v1
The main paper refers to supporting information, but no separate supporting information file was found among the files available from the ChemRxiv record
| Identifier | [1]PF₅CN |
|---|---|
| ¹H NMR (400 MHz, CDCl₃) | δ = 0.90–0.93 (m, 3H, NC₅H₁₀CH₃), 1.33 (m, 6H, NC₂H₄C₃H₆CH₃), 2.93 (s, 3H, NCH₃), 3.23 (t, 2H, NCH₂C₅H₁₁, J = 7.8 Hz), 5.21 (s, 5H, Cp-H₅), 5.64 (d, 2H, Ar-H₂, J = 6.72 Hz), 5.77 (t, 1H, Ar-H, J = 5.6 Hz), 5.91–5.94 (m, 2H, Ar-H₂) |
| ¹⁹F NMR (376 MHz, CDCl₃) | δ = −77.5 (dquin, 1F), −48.4 (dd, 4F) |
| ³¹P NMR (162 MHz, CDCl₃) | δ = −160 (dquin) |
| FT-IR (cm⁻¹) | 552, 555, 596, 656, 693, 728, 807, 895, 914, 942, 1002, 1090, 1105, 1119, 1150, 1170, 1197, 1260, 1298, 1322, 1371, 1415, 1431, 1475, 1556, 1714, 2210 (CN), 2859, 2930, 2955, 3115 |
| Elemental analysis | Calcd for C₁₉H₂₇N₂RuPF₅: C, 44.71; H, 5.29; N, 5.49. Found: C, 44.96; H, 5.12; N, 5.92 |
| Viscosity (25 °C) | 1.08 Pa·s; Newtonian liquid |
| Differential scanning calorimetry (10 °C min⁻¹) | Tg = −65 °C; no other transition was observed |
| Thermogravimetric analysis (3 °C min⁻¹, N₂) | Tdec = 173 °C, defined at 3 % weight loss; two weight-loss steps of 12 and 62 wt % |
| ¹H NMR (CD₃CN), reaction monitoring | Conversion reached 64 % after about 20 min, corresponding to a cation dissociation ratio of 32 %, and then remained nearly constant; product composition: [1](PF₅CN)₀.₃₆[CpRu(PF₅CN)₂(PhNMeHex)]₀.₆₄ |
|---|---|
| UV–Vis (30 min irradiation; 30 min heating) | Absorption around 360 nm increased after irradiation, consistent with formation of the cyano-coordinated complex, and returned to the starting-material spectrum after heating |
| FT-IR | The very weak CN stretching band at 2208 cm⁻¹ shifted to 2224 cm⁻¹ and increased in intensity after irradiation, consistent with coordination of the CN group to Ru; heating restored the original spectrum |
| Spectroscopy, neat-state thermal recovery (120 °C, 10 min) | All spectra returned to their initial forms |
| ¹H NMR, neat-state thermal recovery at room temperature | Cation dissociation ratio decreased to 16 % after 2 h and 7 % after 24 h |
| ¹H NMR (CD₃CN), thermal recovery after dissolution | Cation dissociation ratio was 26 % after 6 h and 22 % after 24 h |
| Ionic conductivity (25 °C) | 7.6 × 10⁻⁵ S cm⁻¹ before irradiation; 3.76 × 10⁻⁶ S cm⁻¹ after 5 min irradiation; further irradiation caused little additional change; heating at 120 °C restored the pre-irradiation value |
| Temperature-dependent ionic conductivity (0–120 °C), VFT fit before irradiation | σ25 °C = 6.9 × 10⁻⁵ S cm⁻¹; Ea = 0.32 meV; A = 4.8 × 10⁴ S K¹ᐟ² cm⁻¹; T0 = 85 K |
| Temperature-dependent ionic conductivity after 1 h irradiation at 10 °C | During heating, the Arrhenius plot was linear up to about 41 °C and lay below the pre-irradiation plot; a slope change occurred at higher temperatures; conductivity above 110 °C and during subsequent cooling returned to the original values |
| Ionic-conductivity cycle protocol | Conductivity at 25 °C was measured during alternating UV irradiation at 10 °C for 15 min and heating at 120 °C for 30 min |
| Ionic-conductivity reaction-monitoring and temperature-dependence plots | Filled and open circles denote measurements after photoirradiation and heating, respectively; the temperature-dependence plot distinguishes heating before photoirradiation, heating after photoirradiation and subsequent cooling; the pre-irradiation dashed line is the VFT fit and the post-irradiation dashed line is a guide for the eye; image data were not transcribed |
| ¹H NMR (400 MHz, CDCl₃) | δ = 0.88–0.93 (m, 3H, NC₅H₁₀CH₃), 1.30–1.35 (m, 6H, NC₂H₄C₃H₆CH₃), 2.92 (s, 3H, NCH₃), 3.30 (t, 2H, NCH₂C₅H₁₁, J = 7.2 Hz), 5.20 (s, 5H, Cp-H₅), 6.65–6.71 (m, 3H, Ar-H₃), 7.20–7.24 (m, 2H, Ar-H₂) |
|---|---|
| ¹H NMR (400 MHz, CD₃CN) | δ = 0.90–0.98 (m, 3H, NC₅H₁₀CH₃), 1.30–1.38 (m, 6H, NC₂H₄C₃H₆CH₃), 2.91 (s, 3H, NCH₃), 3.33 (t, 2H, NCH₂C₅H₁₁, J = 7.6 Hz), 4.30 (s, 5H, Cp-H₅), 6.61–6.73 (m, 3H, Ar-H₃), 7.17–7.21 (m, 2H, Ar-H₂) |
| ESI–MS (CH₃CN) | m/z calcd for [RuCp(PF₅CN)₂(PhNMeHex)]⁻: 662.0486; found: 662.0505 |
| Identifier | [2]Cl |
|---|---|
| ¹H NMR (400 MHz, CD₃CN) | δ = 0.86 (t, 3H, C₇H₁₄CH₃, J = 7.08 Hz), 1.20–1.35 (m, 12H, CH₂C₆H₁₂CH₃), 2.46 (t, 2H, CH₂C₇H₁₄, J = 8.00 Hz), 5.43 (s, 5H, Cp-H₅), 6.13–6.26 (m, 5H, Ar-H₅) |
| Identifier | [2]PF₅CN |
|---|---|
| ¹H NMR (400 MHz, CDCl₃) | δ = 0.89 (t, 3H, C₇H₁₄CH₃, J = 6.72 Hz), 1.27–1.37 (m, 12H, CH₂C₆H₁₂CH₃), 2.49 (t, 2H, CH₂C₇H₁₄, J = 7.80 Hz), 5.37 (s, 5H, Cp-H₅), 6.08–6.17 (m, 5H, Ar-H₅) |
| ¹⁹F NMR (376 MHz, CDCl₃) | δ = −77.4 (dquin, 1F), −48.4 (dd, 4F) |
| ³¹P NMR (162 MHz, CDCl₃) | δ = −160 (dquin) |
| FT-IR (cm⁻¹) | 552, 578, 651, 693, 723, 809, 916, 1007, 1061, 1108, 1154, 1378, 1416, 1457, 1504, 1526, 1732, 2208 (CN), 2855, 2926, 3117 |
| Elemental analysis | Calcd for C₂₀H₂₈NRuPF₅: C, 47.15; H, 5.50; N, 2.75. Found: C, 47.34; H, 5.39; N, 3.03 |
| Viscosity (25 °C) | 0.34 Pa·s; Newtonian liquid |
| Differential scanning calorimetry (10 °C min⁻¹) | Tg = −70 °C; no other transition was observed |
| Thermogravimetric analysis (3 °C min⁻¹, N₂) | Tdec = 178 °C, defined at 3 % weight loss; two weight-loss steps of 15 and 65 wt % |
| ¹H NMR (CD₃CN), reaction monitoring | Conversion reached 66 %, corresponding to a cation dissociation ratio of 33 %; product composition: [2](PF₅CN)₀.₃₄[RuCp(PF₅CN)₂(PhOctyl)]₀.₆₆ |
|---|---|
| ¹H NMR (CD₃CN), neat-state photoproduct content at room temperature | Cation dissociation ratio: 36 % immediately after irradiation, 33 % after 6 h, and 32 % after 24 h |
| ¹H NMR (CD₃CN), thermal recovery after dissolution | No thermal back reaction was observed |
| UV–Vis (30 min irradiation; 30 min heating) | Absorption around 360 nm increased after irradiation; heating decreased the absorption slightly, but did not restore the initial spectrum |
| FT-IR | The CN stretching band at 2208 cm⁻¹ shifted to 2224 cm⁻¹ and increased in intensity after irradiation, consistent with coordination of the CN group; after heating, a strong band assignable to an anion-derived decomposition product appeared at 2120 cm⁻¹ |
| ¹H NMR (400 MHz, CDCl₃) | δ = 0.85–0.90 (m, 3H, C₇H₁₄CH₃), 1.27–1.36 (m, 12H, CH₂C₆H₁₂CH₃), 2.60 (t, 2H, CH₂C₇H₁₅, J = 8.0 Hz), 4.17 (s, 5H, Cp-H₅), 7.16–7.19 (m, 5H, Ar-H₅) |
|---|---|
| ¹H NMR (400 MHz, acetone-d₆) | δ = 0.85–0.89 (m, 3H, C₇H₁₄CH₃), 1.28–1.42 (m, 12H, CH₂C₆H₁₂CH₃), 2.63 (t, 2H, CH₂C₇H₁₅, J = 7.6 Hz), 4.34 (s, 5H, Cp-H₅), 7.14–7.28 (m, 5H, Ar-H₅) |
| ESI–MS (CH₃CN) | m/z calcd for [RuCp(PF₅CN)₂(PhOctyl)]⁻: 661.0533; found: 661.0543 |
| Thermogravimetric analysis (3 °C min⁻¹, N₂), [1]PF₆ | Tdec = 257 °C, defined at 3 % weight loss |
|---|---|
| Thermogravimetric analysis (3 °C min⁻¹, N₂), [2]PF₆ | Tdec = 264 °C, defined at 3 % weight loss |