Interestingly, an excellent correlation can be established between the Ir-Cipso distances obtained from X-ray diffraction studies and the orbital contribution (ΔE orb ) to the overall interaction between the [Ir(POCOP)] fragment and the additional ligands (Figure ). This contribution was estimated by means of the Energy Decomposition Analysis method, as discussed in detail in the Supporting Information (Table ), and represents a clear manifestation of the concept of trans influence and its orbital essence.