C─H Activation Enables the Construction of New Bis‐Polyaryl Phenylpyridine Ruthenium Complexes: Conjugation and Rigidity Synergistic Effect for Advanced Electrochemiluminescence

Abstract The access to bench‐stable organometallic compounds unfolds new chemical space for medicinal and material sciences. In particular, stable organoruthenium compounds with constitutional and stereoisomeric forms for subtle regulation of electrochemiluminescence are intriguing and challenging. Here, coordination of polycyclic aromatic hydrocarbons on (2‐phenylpyridine)₂(CO)₂Ru complex allows access to bis‐polyaryl phenylpyridine (BPP) Ruthenium complex through C─H activation strategy and coupling reactions for installation of the functionalities with steric and electronic purposes. The photoluminescence and electrochemiluminescence of BPP Ru complexes are affected by the actual polycyclic aromatic hydrocarbons inherent properties. The anthracene derivatized BPP Ru complex (BPP‐Ant) shows the best ECL performance and reveals an enormous ECL quantum efficiency of 1.6‐fold higher than the golden standard Ru(bpy)₃²⁺. The unprecedentedly high efficiency is due to the best compromise between the structural conjugation and molecular rigidity from BPP‐Ant providing a providential energy gap that facilitated the feasibility of electron transfer and favored the radiative energy release by experimentally and DFT calculations. Moreover, PL and spooling ECL spectroscopies are used to track and link multiple emission peaks of BPP‐Ant at 445, 645, and 845 nm to different emissive species. These discoveries will add a new member to the efficient ECL ruthenium complex family and bring more potentials.