| Differential scanning calorimetry, transition entropy to the ionic plastic-crystal phase | 36.8–54.0 J mol⁻¹ K⁻¹ for all salts except [1]BMe(CN)₃ |
|---|---|
| Polarized optical microscopy, ionic plastic-crystal phases | Disappearance of birefringence |
| Differential scanning calorimetry, melting | Not observed |
| Thermogravimetry (3 K min⁻¹, N₂), BE(CN)₃-salt decomposition profiles | A single major mass-loss step, attributable to complete or partial loss of the anion together with dissociation of the benzene ligand |
| Thermogravimetry (3 K min⁻¹, N₂), BE₂(CN)₂-salt decomposition profiles | Two mass-loss steps: the first was attributable to the loss of two cyano groups and the second to decomposition of the remaining part of the anion |
| Differential scanning calorimetry phase sequences and thermogravimetry traces | Image data were not transcribed |
| Single-crystal X-ray packing diagrams (90 K) | Image data were not transcribed |
| Phase-transition temperature correlations with anion radius ratio and Δr/rav | Image data were not transcribed |
Ryota Inoue, Haruka Koshino, Yasuhide Iwamoto, Kenta Hongo, Tomoyuki Mochida. “Phase behavior and solid-state photoreactivity of organometallic ionic plastic crystals with cyanoborate anions.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007790/v1
The main paper refers to supporting information, but no separate supporting information file was found among the files available from the ChemRxiv record
| Differential scanning calorimetry, transition to the ionic plastic-crystal phase | Tc = 276.8 K; ionic plastic-crystal phase range: 277–462 K |
|---|---|
| Thermogravimetry (3 K min⁻¹, N₂), thermal decomposition | Tdec = 462 K, defined at 3 wt% mass loss |
| Powder X-ray diffraction (383 K, ionic plastic-crystal phase) | CsCl-type structure with strong 100 and 110 reflections; a = 7.47 Å |
| ¹H NMR (CDCl₃; 365 nm irradiation at 293 K in the ionic plastic-crystal phase, early irradiation stage) | Minor Cp signals distinct from those of the cubane-type complex; the signals gradually decreased upon prolonged photoirradiation |
|---|---|
| Benzene retained in the photoproduct (365 nm irradiation at 293 K in the ionic plastic-crystal phase for 24 h) | Approximately 40 % of the initial cation content; 17 % after vacuum drying for 3 h |
| ¹H NMR reaction monitoring, conversion over irradiation time (365 nm irradiation at 293 K in the ionic plastic-crystal phase) | Image data were not transcribed |
| Differential scanning calorimetry, Phase III transition to the ionic plastic-crystal phase | Tc = 299.3 K; ΔS = 38.5 J mol⁻¹ K⁻¹ |
|---|---|
| Differential scanning calorimetry, as-grown Phase II transition to the ionic plastic-crystal phase | Tc = 306.0 K; ΔS = 47.7 J mol⁻¹ K⁻¹ |
| Differential thermal analysis (3 K min⁻¹, N₂), thermal decomposition | Tdec = 397 K, assigned from the exothermic peak preceding mass loss |
| Powder X-ray diffraction (383 K, ionic plastic-crystal phase) | CsCl-type structure with strong 100 and 110 reflections; a = 7.39 Å |
| Single-crystal X-ray diffraction (90 K, Phase II) | Space group P2₁/n; Z = 4; nonalternating cation–anion arrangement characterized by cation–cation contacts in addition to cation–anion contacts |
| Differential scanning calorimetry, transition to the ionic plastic-crystal phase | Tc = 378.2 K; total ΔS = 19.2 J mol⁻¹ K⁻¹ |
|---|---|
| Thermogravimetry (3 K min⁻¹, N₂), thermal decomposition | Tdec = 461 K, defined at 3 wt% mass loss |
| Powder X-ray diffraction (383 K, ionic plastic-crystal phase) | CsCl-type structure with strong 100 and 110 reflections; a = 7.55 Å |
| Single-crystal X-ray diffraction (90 K, Phase III) | Space group P2₁/c; Z = 4; alternating cation–anion arrangement with each cation surrounded by eight anions; cations orientationally disordered over two opposite orientations, with overlapping Cp- and benzene-ring sites of 0.5 occupancy each |
| Single-crystal X-ray diffraction (90 K), Ru–B distances | Cation I: r = 5.84–6.76 Å, Δr = 0.33 Å; Cation II: r = 5.42–7.96 Å, Δr = 0.65 Å; rav = 6.90 Å |
| Differential scanning calorimetry, transition to the ionic plastic-crystal phase | Tc = 295.1 K |
|---|---|
| Thermogravimetry (3 K min⁻¹, N₂), thermal decomposition | Tdec = 451 K, defined at 3 wt% mass loss |
| Powder X-ray diffraction (383 K, ionic plastic-crystal phase) | CsCl-type structure with strong 100 and 110 reflections; a = 7.27 Å |
| FT-IR | Absorption band at 2107 cm⁻¹ attributable to unidentified decomposition products |
|---|---|
| ¹H NMR and ESI–MS, photoproduct composition | The product contained the dinuclear complex [Ru₂Cp₂{BF₂(CN)₂}₃]⁻, but its amount could not be determined |
| Differential scanning calorimetry, transition to the ionic plastic-crystal phase | Tc = 372.8 K |
|---|---|
| Thermogravimetry (3 K min⁻¹, N₂), thermal decomposition | Tdec = 430 K, defined at 3 wt% mass loss |
| Powder X-ray diffraction (383 K, ionic plastic-crystal phase) | CsCl-type structure with strong 100 and 110 reflections; a = 7.85 Å |
| Single-crystal X-ray diffraction (90 K, Phase II) | Space group Pnma; Z = 4; alternating cation–anion arrangement with each cation surrounded by eight anions; cations orientationally disordered over two opposite orientations, with overlapping Cp- and benzene-ring sites of 0.5 occupancy each |
| Single-crystal X-ray diffraction (90 K), Ru–B distances | r = 5.58–7.96 Å; rav = 6.79 Å; Δr = 0.87 Å |
| ESI–MS | m/z calcd: 97.0165; found: 97.0165 |
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