Table 3.
Selected bond lengths (Å), bond angles (º), and torsion angles (º) optimized for complexes in S0 and T1 using TDDFT in ethanol except for Ru(2H)dcbpy where ∆SCF data are reported.
| Rubpy | Rudcbpy | Rudamidebpy | RudMebpy | Ru(2H)dcbpy | Ru(2CO)dcbpy | ||||
|---|---|---|---|---|---|---|---|---|---|
| S0 | a | B3LYP | PBE0 | B3LYP | B3LYP | B3LYP | PBE0 | B3LYP | B3LYP |
| Ru-P1 | 2.351 | 2.448 | 2.392 | 2.454 | 2.451 | 2.448 | 2.391 | 2.364 | 2.561 |
| Ru-P2 | 2.349 | 2.449 | 2.394 | 2.453 | 2.450 | 2.449 | 2.392 | 2.364 | 2.560 |
| Ru-N1 | 2.091 | 2.174 | 2.139 | 2.168 | 2.169 | 2.173 | 2.137 | 2.152 | 2.160 |
| Ru-N2 | 2.135 | 2.246 | 2.196 | 2.244 | 2.246 | 2.246 | 2.198 | 2.186 | 2.161 |
| Ru-H | 1.623 | 1.613 | 1.613 | 1.610 | 1.611 | 1.613 | 1.613 | 1.635, 1.652 | |
| Ru-C | 1.816 | 1.861 | 1.852 | 1.865 | 1.864 | 1.862 | 1.852 | 1.918, 1.919 | |
| P1-Ru-P2 | 174.701 | 170.034 | 168.952 | 168.954 | 169.194 | 170.099 | 169.164 | 160.234 | 176.817 |
| N1-Ru-N2 | 75.040 | 74.733 | 75.579 | 74.858 | 74.772 | 74.544 | 75.413 | 75.801 | 76.650 |
| N1-C-C-N2 | −2.869 | 0.181 | 0.616 | -0.122 | 0.201 | 1.100 | 1.002 | 0.172 | −0.112 |
| T1 | |||||||||
| Ru-P1 | 2.414 | 2.445 | 2.440 | 2.408 | 2.406 | 2.556 | |||
| Ru-P2 | 2.402 | 2.518 | 2.521 | 2.404 | 2.406 | 2.557 | |||
| Ru-N1 | 2.102 | 2.140 | 2.137 | 2.101 | 2.219 | 2.144 | |||
| Ru-N2 | 2.097 | 2.161 | 2.153 | 2.089 | 2.218 | 2.149 | |||
| Ru-H | 1.635 | 1.627 | 1.628 | 1.636 | 1.604, | ||||
| 1.630 | |||||||||
| Ru-C | 1.884 | 1.896 | 1.895 | 1.883 | 1.920, | ||||
| 1.923 | |||||||||
| P1-Ru-P2 | 142.144 | 143.280 | 143.788 | 143.024 | 169.175 | 178.093 | |||
| N1-Ru-N2 | 78.876 | 77.377 | 77.590 | 78.864 | 74.716 | 77.505 | |||
| N1-C-C-N2 | −2.769 | 4.195 | 3.189 | −2.046 | 0.114 | −0.874 | |||
*
N1 is trans to CO and N2 is trans to H.
a
Experimental data taken from ref. [36]