Table 1.
Relative Gibbs free energies [kcal ⋅ mol−1] of the selected conformations of unsubstituted hexa‐, hepta‐, and octaphyrins with distinct global charge and oxidation states.[a]
|
|
[26]2− |
[26] |
[28] |
[28]2+ |
|
[32]4− |
[32] |
[32]3+ |
|
[36]2− |
[36] |
[36]2+ |
[38]2+ |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
|
R |
0.0 |
8.1 |
7.6 |
0.0 |
H |
0.0 |
29.8 |
0.8 |
H a |
12.2 |
33.4 |
13.7 |
0.0 |
|
D |
27.7 |
0.0 |
0.0 |
8.1 |
M |
24.2 |
11.9 |
0.0 |
H b |
17.0 |
49.8 |
31.6 |
5.8 |
|
T |
7.1 |
27.8 |
28.7 |
9.5 |
F |
[b] |
0.0 |
7.5 |
M a |
1.2 |
27.9 |
4.6 |
10.9 |
|
M |
[b] |
21.5 |
5.9 |
3.8 |
– |
– |
– |
– |
M b |
21.4 |
49.7 |
27.9 |
11.0 |
|
F |
50.3 |
17.9 |
8.8 |
[b] |
– |
– |
– |
– |
F a |
12.6 |
0.0 |
1.5 |
2.3 |
|
– |
– |
– |
– |
– |
– |
– |
– |
– |
F b |
0.0 |
14.5 |
0.0 |
9.7 |
[a] Gibbs free energies at the M06‐2X/6‐311+G(d,p)//CAM‐B3LYP/6‐311G(d,p) level of theory. [b] The optimization of 28F2+ , 26M2− , and 32F4− did not lead to minimum geometry compatible with these conformations; instead it led to untwisted geometries.