Table 4.
Parameters for three configuration simulations of K3[Fe(CN)6], K4[Fe(CN)6]50, [Fe(tpp)(ImH)2] and [Fe(tpp)(ImH)2]Cl
| Compound | ˆ Configuration Separations | MLCT Mixing* Parameters | LMCT Mixing* Parameters | Ligand Field* | ||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| EG2 | EF2 | EG3 | EF3 | d5L--d6T(b1) | d5L--d6T(a1) | d5L--d6T(b2) | d5L--d6T(e1) | d6-d7LT(b1) | d6-d7LT(a1) | d6-d7LT(b2) | d6-d7LT(e1) | 10Dq | Dt | Ds | ||
| K3[Fe(CN)6] 50 | 1.00 | 0.50 | -1.00 | -1.50 | 0.9 | 0.9 | 2.0 | 2.0 | 1.9 | 1.9 | 0.0 | 0.0 | 3.7 | 0.0 | 0.0 | |
| K4[Fe(CN)6] 50 | 2.06 | 1.56 | 2.00 | 0.00 | 0.8 | 0.8 | 1.6 | 1.6 | 1.7 | 1.7 | 0.0 | 0.0 | 3.9 | 0.0 | 0.0 | |
| [Fe(tpp)(ImH)2]Cl | 1.40 | 1.60 | 0.00 | 0.00 | 0.0 | 0.0 | 0.7 | 1.3 | 4.4 | 3.2 | 1.0 | 2.7 | 2.2 | 0.028 | 0.0 | |
| [Fe(tpp)(ImH)2] | 1.40 | 1.60 | 1.00 | -1.00 | 0.0 | 0.0 | 0.0 | 0.8 | 2.8 | 2.8 | 1.6 | 2.9 | 1.63 | 0.008 | 0.019 | |
*
These parameters are for the 2p6 initial state and 2p5 final sate. These ligand field parameters and T and Δ will decrease upon going to the final state and the effects of changing their values in the 2p5 final state have been evaluated, see Figure S9. It is found that final state changes do not affect the results of the DOC analysis of the initial state in these highly covalent systems.
ˆ
These parameters are defined relative to the dN-1 configuration. i.e. EG1=0.