Table 2.
Calculated Δoct, sum of cobalt p and d character in MOs contributing to the V2C region, and V2C XES oscillator strength for low-spin octahedral cobalt(III) complexes.
| Δoct (Eh) a | ΣCo p% b | ΣCo d% b | DFT-calculated Oscillator Strength (a.u.) c |
|
|---|---|---|---|---|
| [Co(CN)6]3− | 0.147 | 58.8 | 391.5 | 8.49×10−3 |
| [Co(dmgH)2(py)2]+ | 0.122 | 40.8 | 389.9 | 7.29×10−3 |
| [Co(en)3]3+ | 0.114 | 40.9 | 389.1 | 7.14×10−3 |
| [Co(NH3)6]3+ | 0.114 | 41.8 | 389.4 | 7.12×10−3 |
| [Co(NH3)6]3+ (*) | 0.0980 | 41.5 | 385.7 | 6.00×10−3 |
| [Co(acac)3] | 0.0862 | 35.7 | 385.9 | 6.69×10−3 |
| [Co(ox)3]3− | 0.0780 | 35.9 | 384.9 | 6.41×10−3 |
| [Co(OH)6]3− | 0.0669 | 35.1 | 383.6 | 5.52×10−3 |
| [CoF6]3− | 0.0632 | 36.1 | 378.6 | 5.95×10−3 |
| [Co(dtc)3] | 0.0680 | 50.3 | 398.9 | 5.20×10−3 |
| [Co(SCN)6]3− | 0.0467 | 48.6 | 396.7 | 4.19×10−3 |
| [CoCl6]3− | 0.0430 | 44.6 | 387.6 | 3.67×10−3 |
Δoct is determined as the energy level difference between the average energy of eg-derived d orbitals and that of t2g-derived d orbitals from DFT calculations.
ΣCo p% and ΣCo d% represent the sum of cobalt p and d character in donor MOs in the V2C region, respectively, based on the Löwdin population analysis.
The DFT-calculated oscillator strength in the V2C region encompass the electric dipole, magnetic dipole, and electric quadrupole contributions. * The two [Co(NH3)6]3+ are based on coordinates of crystal structure (Δoct = 0.114) and a DFT geometry-optimized structure (Δoct = 0.0980), respectively (see SI for details of coordinates).