The Multichromophore Approach: Prolonged Room‐Temperature Luminescence Lifetimes in Ru II Complexes Based on Tridentate Polypyridine Ligands

A new family of ruthenium(II) complexes with multichromophoric properties was prepared based on a “chemistry‐on‐the‐complex” synthetic approach. The new compounds are based on tridentate chelating sites (tpy‐type ligands, tpy=2,2′:6′,2′′‐terpyridine) and most of them carry appended anthryl chromophores. Complexes 2 a and 2 b were synthesized through the Pd‐catalyzed Suzuki coupling reaction between 9‐anthrylboronic acid and the chloro ligands on the presursor species 1 a and 1 b , respectively. The monocoupling product 2 c was also synthesized as the starting complex for a dimetallic complex under optimized Suzuki coupling conditions. The palladium(0)‐catalyzed homocoupling reaction on complexes 1 a and 2 c led to dimetallic Ru II species 2 d and 2 e , respectively. The solid structures of complexes 2 a and 2 b were characterized by X‐ray diffraction. The absorption spectra, redox behavior, luminescence properties (both at room temperature and at 77 K), and transient absorption spectra and decays of 2 a – e were investigated. The absorption spectra of all new species are dominated by ligand‐centered (LC) bands in the UV region and metal‐to‐ligand charge‐transfer (MLCT) bands in the visible region. The new compounds undergo reversible metal‐centered oxidation processes and several ligand‐centered reduction processes, which have been assigned to specific sites. The complexes exhibit luminescence both at room temperature in fluid solution and at 77 K in rigid matrices; the emission was attributed to 3 MLCT states at room temperature and to the lowest‐lying anthracene triplet ( 3 An) at low temperature, except for 2 c , which does not contain any anthryl chromophore and whose low temperature emission is also of MLCT origin. The luminescence lifetimes of complexes 2 a – d showed that multichromophoric behavior occurs in these species, allowing the luminescence lifetime of the Ru II ‐based chromophores to be prolonged to the microsecond timescale, with the anthryl groups behaving as energy‐storage elements for the repopulation of the 3 MLCT state. Nanosecond transient‐absorption spectroscopy confirmed the equilibration process between the triplet MLCT and An levels at room temperature. Thermodynamic and kinetic factors governing the equilibration time and the lifetime of the equilibrated excited state are discussed.