Experimentally, a low-energy limit of E00 for MLCT can be estimated as 700 nm (14285 cm -1 , 1.77 eV) from the intersection of the absorption and emission spectra recorded in MeCN. Therefore, excitation with 660 nm light (15152 cm -1 , 1.88 eV) implies dissipation of only 110 meV, equivalent to only 6% of the incident light energy (Figure ). There is growing interest in anti-dissipative strategies to improve solar-energy conversion or any photocatalytic efficiencies. Intersystem crossing has been identified as a major source of dissipation with losses of 20-30% of the incident light energy, thus limiting the efficiency of light harvesting strategies. In this context, the (N,C,N)-Bi(I) complexes can provide interesting opportunities due to the small S-T energy gaps and intense ground-state absorptions of S0 → S1 transitions (molar absorptivity of around 3620 M -1 cm -1 at 630 nm) with minimal energy losses associated to ISC, affording, for example, synthetically salient excited-state redox potentials. In fact, Rehm-Weller methods were employed to estimate the redox potential of the excited state species. Combining the low-energy limit of E00 for 3 MLCT of 1.77 eV and the ground state redox potential of the Bi II/I redox couple (E1/2 = -0.85 V vs Fc +/0 in MeCN) an excited state redox potential of -2.62 V vs Fc +/0 in MeCN can be obtained.