Table 1.
Summary of experimentally and theoretically determined HOMO and LUMO energies of 4, 5, 14, and 15.
|
|
E HOMO,exp. [eV][a] |
E LUMO,exp. [Eg] [eV][b] |
E HOMO,theo. [eV][c] |
E LUMO,theo. [Eg] [eV][c] |
|---|---|---|---|---|
|
5 |
−5.01 |
−2.04 [3.02] |
−4.59 |
−1.11 [3.48] |
|
4 |
−4.71 |
−2.16 [2.55] |
−4.54 |
−1.85 [2.69] |
|
14 |
−4.80 |
−2.66 [2.14] |
−4.32 |
−2.02 [2.20] |
|
15 |
−4.62 |
−2.73 [1.89] |
−4.27 |
−2.33 [1.94] |
[a] Electrochemically determined oxidation and reduction potentials referring to Fc/Fc+ as internal standard (E HOMO(fc)=−4.8 eV): E HOMO,exp=−4.8 eV−E 1/2,ox1. [b] Determined HOMO and LUMO energies based on the optical HOMO–LUMO energy gap [Eg]: E LUMO,exp=E HOMO,exp+Eg,opt. [c] Calculated HOMO and LUMO energies, level of theory: def2‐TZVPP/B3LYP, for carthesian coordinates (XYZ) of optimized geometries see Table S1–S4.