This case study on a series of monomeric, dimeric and polymeric Cu(I) chlorido NHC-picolyl complexes shows that cuprophilic interactions can ensure strong spin-orbit coupling for fast (reverse)intersystem-crossing T1 ↔ S1 and T1 → S0, and therefore can serve as a design motif for the construction of highly efficient Cu(I)-based TADF or T1 emitters.