TABLE 4.
Results of NBO analysis (natural charge (Q), bond order (BO) and delocalization energy (E 2)) determined by DFT method at the B3LYP/SDD level for 1–3
| Bond | BO | ||
|---|---|---|---|
| 1 | 2 | 3 | |
| M―OPT | 0.420 | ― | ― |
| M―ODMF | 0.187 | ― | ― |
| M―N[ a ] | 0.376 |
0.297/0.281/0.284(NN‐Py) 0.187(Nax) |
0.298 |
| M―Cl | ― |
0.582 ― |
0.229 |
| Atom/Q | 1 | 2 | 3 |
|---|---|---|---|
| M (metal) | 0.810 | 0.814 | 0.851 |
| OPT | −1.039 | — | — |
| OMDF | −0.653 | — | — |
| N[ a ] | −0.524 |
−0.576/−0.554/−0.585(Naxial) −1.044(NN‐Py [ b ]) |
−0.356 |
| Cl | — | −0.553 | −0.724 |
| Donor–acceptor interactions | |||
|---|---|---|---|
| Compound | Donor | Acceptor | E 2(kcal/mol) |
| 1 | LP OPT | LP[ a ] Co | 80.83 |
| LP ODMF | LP[ a ] Co | 28.60 | |
| LP N | LP[ a ] Co | 49.94 | |
| 2 | |||
| LP Neq | LP[ a ] Cu | 40.53/41.06(NN‐Py)/36.77 | |
| LP Nax | LP[ a ] Cu | 23.47 | |
| LP Cl | LP[ a ] Cu | 87.21 | |
| 3 | |||
| LP N | LP[ a ] Cu | 41.66/41.72 | |
| LP Cl | LP[ a ] Cu | 29.01/29.03 | |
a
N is nitrogen atom of pyridine (for 1 and 2) or pyrazole (for 3) ring coordinated to metal.
b
NN‐Py is negative nitrogen (N−) of (O)P(N−—Py) segment of PT ligand coordinated to metal for 2.