Table 1.
Selected Structural Parameters of 2–7.
| Complex | Metal ion | Average Mn-oxo distance (Å) | Average Mn–Mn distance (Å) | Oxidation state |
|---|---|---|---|---|
| Mn1 | 1.919(4) | 3.2 | Mn(III) | |
| 2 | Mn2 | 2.157(3) | 3.3 | Mti(II) |
| MnII3MnIIIO | Mn3 | 2.041(4) | 3.2 | Mn(II) |
| Mn4 | 2.049(3) | 3.5 | Mti(II) | |
|
| ||||
| Overall Average | 2.04 ± 0.10 | 3.31 ± 0.22 | ||
|
| ||||
| Mn1 | 2.068(2) | 3.3 | Mn(III) | |
| 3 | Mn2 | 2.095(3) | 3.2 | Mri(II) |
| MnII2MnIII2O | Mn3 | 1.980(3) | 3.2 | Mn(III) |
| Mn4 | 2.048(3) | 3.5 | Mn(II) | |
|
| ||||
| Overall Average | 2.05 ± 0.05 | 3.32 ± 0.21 | ||
|
| ||||
| Mn1 | 1.91 ± 0.07 | 3.0 | Mn(III) | |
| 4 | Mn2 | 2099(2) | 3.3 | Mn(II) |
| MnII2MnIII2O2 | Mn3 | 2.174(2) | 3.3 | Mti(II) |
| Mn4 | 1.84 ± 0.02 | 3.3 | Mn(III) | |
|
| ||||
| Overall Average | 1.96 ±0.14 | 3.24 ± 0.29 | ||
|
| ||||
| Mn1 | 1.88 ±0.03 | 3.1 | Mn(III) | |
| 5 | Mn2 | 1.89 ±0.05 | 3.1 | Mn(III) |
| MnIII4O3 | Mn3 | 1.884 ± 0.004 | 3.1 | Mn(III) |
| Mn4 | 2.02 ± 0.12 | 2.8 | Mn(III) | |
|
| ||||
| Overall Average | 1.93 ± 0.09 | 3.03 ± 0.21 | ||
|
| ||||
| Mn1 | 2.04 ± 0.19 | 3.0 | Mn(III) | |
| 6 | Mn2 | 1.86 ±0.02 | 2.9 | Mn(IV) |
| MnIII2MnIV2O4 | Mn3 | 1.93 ± 0.07 | 2.9 | Mn(IV) |
| Mn4 | 2.01 ±0.16 | 2.9 | Mn(III) | |
|
| ||||
| Overall Average | 1.96 ± 0.13 | 2.92 ± 0.10 | ||
|
| ||||
| Mn1 | 1.87 ± 0.02 | 2.9 | Mn(IV) | |
| 7 | Mn2 | 1.88 ± 0.01 | 2.9 | Mn(IV) |
| MnIII2MnIV2O4 | Mn3 | 2.00 ± 0.10 | 2.9 | Mn(III) |
| Mn4 | 2.06 ± 0.15 | 2.9 | Mn(III) | |
|
| ||||
| Overall Average | 1.95 ± 0.09 | 2.91 ± 0.09 | ||
a
The bond distance with the corresponding XRD esd in parentheses are given for Mn centers with one Mn–O bond. The average Mn–O distance with a standard deviation are given for Mn centers with multiple Mn–O bonds. Complexes 5 and 6 have been reported previously.32, 33 These metrics are included here for comparison. The Mn labels for 6 are equivalent to those given in ref. 32, Figure 2c.