Spectroscopy and absolute quantum efficiency of near-infrared electrochemiluminescence for a macrocyclic palladium complex

Abstract

Electrochemiluminescence (ECL) is widely applied as a reliable tool in clinical diagnosis, including immunoassays, cancer biomarker detection, etc. Metal complexes with emission in the near-infrared (NIR) range possess distinct features such as high transmission and minimal tissue auto-absorption, making them versatile for applications in biosensing and other fields. Through ECL spectral studies of an O-linked nonaromatic benzitripyrrin (C^N^N^N) macrocyclic palladium complex (Pd1) with multiple pyrrole structures, we observed emission peaks from the Qx(0,0) and its vibronic Qx(0,1) bands during both photoluminescence (PL) and ECL. Notably, the emission from the Qx(0,1) band was significantly enhanced in the ECL spectrum, demonstrating higher selectivity for near-infrared light at 743 nm. In the ECL annihilation pathway, the appearance of ECL signals showed a strong correlation with the redox processes of the tri-pyrrin structure, revealing a cyclic tri-pyrrin ligand-centered nature with contributions from the metal center. Upon the introduction of tripropylamine (TPrA) and benzoyl peroxide (BPO) coreactants, the ECL signals exhibited enhancements ranging from several hundred to tens of times. Various reaction routes within different coreactant systems are extensively discussed. Additionally, the absolute quantum efficiencies of the Pd1/TPrA coreactant system were determined, showing efficiencies of 0.0032% ± 0.0005% and 0.000074% ± 0.000016% during pulsing and CV scan processes, respectively. This work addresses gaps in the study of palladacycle complexes in ECL and provides insights into the design of NIR luminescent structures that contribute to the fast screening and deep tissue penetration bioimaging techniques.