| ¹H NMR (400 MHz, DMSO-d₆) | δ = 0.75 (t, 2H, BCH₂, J = 8.26 Hz), 2.27 (t, 2H, BCH₂CH₂, J = 8.36 Hz) |
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| ¹¹B NMR (128 MHz, DMSO-d₆) | δ = −31.14 (s) |
| FT-IR (cm⁻¹) | 563, 571, 636, 851, 891, 950, 984, 1013, 1173, 1223, 1328, 1434, 2224 (CN), 2259 (CN), 2930 |
Haruka Koshino, Fumitaka Takeiri, Kunihisa Sugimoto, Tomoyuki Mochida. “Tuning structural order in photogenerated metal-complex solids from ruthenium-containing ionic liquids.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007791/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 | 1a |
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| ¹H NMR (400 MHz, CDCl₃) | δ = 0.91–0.93 (m, 3H, NC₅H₁₀CH₃), 1.02–1.06 (m, 2H, BCH₂CH₂CN), 1.28–1.41 (m, 8H, NCH₂C₄H₈CH₃), 2.39–2.43 (m, 2H, BCH₂CH₂CN), 2.95–2.96 (m, 3H, NCH₃), 3.24–3.28 (m, 2H, NCH₂C₅H₁₁), 5.23 (s, 5H, Cp-H₅), 5.63–5.65 (m, 2H, Ar-H₂), 5.81–5.84 (m, 1H, Ar-H), 5.94–5.96 (m, 2H, Ar-H₂) |
| ¹¹B NMR (128 MHz, CDCl₃) | δ = −30.73 (s) |
| FT-IR (cm⁻¹) | 557, 656, 725, 837, 881, 942, 981, 1002, 1089, 1105, 1169, 1197, 1260, 1321, 1372, 1414, 1430, 1474, 1555, 2205 (CN), 2242 (CN), 2858, 2928, 3100 |
| Elemental analysis | Calcd. for C₂₄H₃₀N₅RuB: C, 57.60; H, 6.04; N, 14.00. Found: C, 56.95; H, 6.19; N, 13.82 |
| Differential scanning calorimetry | Glass transition at 215 K |
| TG–DTA (3 K min⁻¹, N₂), thermal decomposition | Tdec = 458 K, defined at 3 % weight loss; single-step weight loss corresponding to loss of the anion and arene ligand: observed, −52 wt %; calcd, −56 wt % |
| Raman spectroscopy | CN stretching bands at 2245 and 2209 cm⁻¹, assigned to B(CN)₃ and B(CH₂CH₂CN), respectively |
| FT-IR | Upon photoirradiation, CN stretching bands at 2240 and 2205 cm⁻¹ were replaced by a single, more intense band at 2224 cm⁻¹; the arene-ring band at 1553 cm⁻¹ split into bands at 1507 and 1599 cm⁻¹ attributable to the dissociated arene ligand; heating restored the original spectrum |
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| ¹H NMR (CDCl₃) | During the photoreaction, the Cp signal shifted, the arene signals disappeared, and new signals due to the dissociated ligand appeared |
| ¹H NMR reaction monitoring, conversion | 92 % after 5 min of irradiation; 100 % after 1 h |
| UV–Vis | Photoirradiation increased absorbance in the 350–450 nm region; heating decreased this absorption; repeated cycles of 30 min photoirradiation and 30 min heating demonstrated reversible spectral changes |
| FT-IR, ¹H NMR and UV–Vis spectra during the photo/thermal reaction | Image data were not transcribed |
| FT-IR, ¹H NMR and UV–Vis | Spectral changes were essentially the same as those of 1a |
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| Identifier | 1b |
|---|---|
| ¹H NMR (400 MHz, (CD₃)₂SO) | δ = 0.92 (t, 3H, NC₅H₁₀CH₃, J = 6.84 Hz), 1.27–1.34 (m, 8H, NCH₂C₄H₈CH₃), 1.54–1.59 (m, 2H, NCH₂CH₂C₄H₉), 2.86 (s, 3H, NCH₃), 3.22 (t, 2H, NCH₂C₅H₁₁, J = 7.74 Hz), 5.15 (s, 5H, Cp-H₅), 5.63 (d, 2H, Ar-H₂, J = 6.64 Hz), 5.74 (t, 1H, Ar-H, J = 5.4 Hz), 5.83 (t, 2H, Ar-H₂, J = 6.10 Hz) |
| ¹⁹F NMR (376 MHz, (CD₃)₂SO) | δ = −78.7 (s) |
| Elemental analysis | Calcd. for C₂₀H₂₆N₂RuF₆O₄S₂: C, 37.67; H, 4.11; N, 4.39. Found: C, 37.72; H, 4.34; N, 4.65 |
| Differential scanning calorimetry | Glass transition at 217 K |
| TG–DTA (3 K min⁻¹, N₂), thermal decomposition | Tdec = 593 K; single-step weight loss |
| Identifier | 1c |
|---|---|
| ¹H NMR (400 MHz, CD₃CN) | δ = 0.92 (t, 3H, NC₅H₁₀CH₃, J = 6.84 Hz), 1.34 (m, 6H, NC₂H₄C₃H₆CH₃), 1.54–1.57 (m, 2H, NCH₂CH₂C₄H₉), 2.86 (s, 3H, NCH₃), 3.22 (t, 2H, NCH₂C₅H₁₁, J = 7.74 Hz), 5.15 (s, 5H, Cp-H₅), 5.63 (d, 2H, Ar-H₂, J = 6.76 Hz), 5.74 (t, 1H, Ar-H, J = 5.48 Hz), 5.81–5.84 (m, 2H, Ar-H₂) |
| ¹⁹F NMR (376 MHz, CD₃CN) | δ = −51.0 (s) |
| Elemental analysis | Calcd. for C₁₈H₂₆N₂RuF₂O₄S₂: C, 40.21; H, 4.87; N, 5.21. Found: C, 40.32; H, 4.89; N, 5.23 |
| Differential scanning calorimetry | Solid-state phase transition at 178.0 K: ΔH = 4.74 kJ mol⁻¹, ΔS = 26.2 J mol⁻¹ K⁻¹; melting at 331.6 K: ΔHm = 26.9 kJ mol⁻¹, ΔSm = 80.5 J mol⁻¹ K⁻¹; glass transition at 213 K on cooling; cold crystallization at 267 K on reheating; Tg/Tm = 0.64 |
| Single-crystal X-ray diffraction (223 K) | Space group P-1; Z = 2; alternating cation–anion arrangement; intermolecular π···π contacts between Cp rings and between benzene rings of adjacent cations with C···C distances of 3.45 and 3.52 Å, respectively; the hexyl groups of the cations adopted all-trans conformations and were aligned parallel to one another; the central N atom of the anion was disordered over three positions with occupancies of 0.463(3):0.307(3):0.230(3), and the –SO₂F groups were likewise disordered over three positions |
| Single-crystal X-ray structure image (223 K) | Image data were not transcribed |
| Identifier | 3 |
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| ¹H NMR (400 MHz, CDCl₃) | δ = 1.09 (t, 2H, BCH₂, J = 7.80 Hz), 2.45 (t, 2H, BCH₂CH₂, J = 7.84 Hz), 4.24 (s, 5H, Cp-H₅) |
| FT-IR (cm⁻¹) | 589, 814, 836, 869, 914, 977, 997, 1100, 1170, 1205, 1293, 1350, 1428, 2223 (CN), 2916, 3101, 3667 |
| Elemental analysis | Calcd. for C₄₄H₃₆N₁₆Ru₄B₄: C, 42.74; H, 2.93; N, 18.13. Found: C, 42.39; H, 2.69; N, 17.79 |
| Optical microscopy | Aggregates of well-defined, cube-shaped crystalline particles |
| Raman spectroscopy | Single, slightly asymmetric band near 2232 cm⁻¹, likely comprising two unresolved components |
| Powder X-ray diffraction, heating at 373 K for 1 h | Pattern was unchanged |
| TG–DTA (3 K min⁻¹, N₂), thermal decomposition | Tdec = 487 K, defined at 3 % weight loss; single-step weight loss corresponding to elimination of cyanoethyl groups: observed, −17.9 wt %; calcd, −17.5 wt % |
| Single-crystal X-ray diffraction (90 K) | Space group P-1; Z = 4; two crystallographically independent cubane molecules in the asymmetric unit; one cyanoethyl group in cubane I was disordered over three positions with occupancies of 0.479(3):0.354(3):0.167(3); one cyanoethyl group in cubane II was disordered over two positions with occupancies of 0.548(7):0.452(7); the methanol molecules occupied voids between neighboring cubane molecules along the c axis |
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| Single-crystal X-ray structure image (90 K) | Image data were not transcribed |
| Optical microscopy and scanning electron microscopy | Image data were not transcribed |
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| Optical microscopy, well-defined cube-shaped crystalline particles in 2, 2′ and 2″ | Not observed |
| Powder X-ray diffraction patterns and PXRD- and ¹H NMR-derived fractions | Image data were not transcribed |
| Powder X-ray diffraction, crystalline phase in 2, 2′ and 2″ | Assigned to cubane-type complex 3 because its diffraction peaks matched those of 3 |
| Raman spectroscopy, coordination environment in 2, 2′ and 2″ | Close similarity to 3 supported the presence of common local Ru–NC–B coordination environments; the data did not establish the overall connectivities |
| Identifier | 2 |
|---|---|
| Elemental analysis | Calcd. for C₄₄H₃₆N₁₆Ru₄B₄: C, 42.74; H, 2.93; N, 18.13. Found: C, 43.19; H, 2.80; N, 18.45 |
| Optical microscopy and scanning electron microscopy | Densely packed morphology on the quartz plates; peeled samples consisted mainly of irregular plate-like fragments |
| Synchrotron powder X-ray diffraction (λ = 0.49592 Å) | Broad halo and sharp diffraction peaks; crystalline cubane-type complex fraction estimated from the integrated areas of the sharp reflections and amorphous halo: approximately 13 %; low-angle peak FWHM = 0.11°; crystallite size estimated using the Scherrer equation: approximately 24 nm |
| ¹H NMR (CD₂Cl₂, immediately after dissolution) | Several Cp-H signals indicated multiple coordination species; cubane-type complex 3 gave a singlet at δ 4.24 ppm and had a semiquantitative solution-derived fraction of 63 %; the remaining signals arose from additional components whose structures could not be assigned; limited reorganization during dissolution could not be excluded |
| ¹H NMR (CDCl₃-soluble portion) | Semiquantitative cubane-type complex 3 fraction: 73 % |
| Raman spectroscopy | Single, slightly asymmetric band near 2232 cm⁻¹, likely comprising two unresolved components |
| Powder X-ray diffraction, heating at 373 K for 1 h | Pattern was unchanged |
| Identifier | 2′ |
|---|---|
| Optical microscopy | Cracks were more prominent than in 2 |
| Synchrotron powder X-ray diffraction (λ = 0.49592 Å) | Broad halo and sharp diffraction peaks; crystalline cubane-type complex fraction estimated from the integrated areas of the sharp reflections and amorphous halo: approximately 19 %; low-angle peak FWHM = 0.10°; crystallite size estimated using the Scherrer equation: approximately 27 nm |
| ¹H NMR (CD₂Cl₂, immediately after dissolution) | Several Cp-H signals indicated multiple coordination species; cubane-type complex 3 gave a singlet at δ 4.24 ppm and had a semiquantitative solution-derived fraction of 56 %; the remaining signals arose from additional components whose structures could not be assigned; limited reorganization during dissolution could not be excluded |
| ¹H NMR (CDCl₃-soluble portion) | Semiquantitative cubane-type complex 3 fraction: 58 % |
| Raman spectroscopy | Single, slightly asymmetric band near 2232 cm⁻¹, likely comprising two unresolved components |
| Powder X-ray diffraction, heating at 373 K for 1 h | Pattern was unchanged |
| Identifier | 2″ |
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| Optical microscopy and scanning electron microscopy | Cracks were more prominent than in 2; peeled samples consisted mainly of irregular plate-like fragments; the surface appeared smoother than that of 2, while the overall morphologies were similar |
| Synchrotron powder X-ray diffraction (λ = 0.79986 Å) | Broad halo and sharp diffraction peaks; crystalline cubane-type complex fraction estimated from the integrated areas of the sharp reflections and amorphous halo: approximately 44 %; low-angle peak FWHM = 0.06°; crystallite size estimated using the Scherrer equation: approximately 45 nm |
| ¹H NMR (CD₂Cl₂, immediately after dissolution) | Several Cp-H signals indicated multiple coordination species; cubane-type complex 3 gave a singlet at δ 4.24 ppm and had a semiquantitative solution-derived fraction of 39 %; the remaining signals arose from additional components whose structures could not be assigned; limited reorganization during dissolution could not be excluded |
| ¹H NMR (CDCl₃-soluble portion) | Semiquantitative cubane-type complex 3 fraction: 54 % |
| Raman spectroscopy | Single, slightly asymmetric band near 2232 cm⁻¹, likely comprising two unresolved components |
| Powder X-ray diffraction, heating at 373 K for 1 h | Pattern was unchanged |
| ¹H NMR, five days after dissolution | The species other than cubane-type complex 3 gradually converted into 3 |
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