Synthesis and Theoretical and Photophysical Study on a Series of Neutral Ruthenium(II) Complexes with Donor–Metal–Accepter Configuration

Abstract

In order to construct a new type of ruthenium(II) terpyridine complexes with activated triplet metal-centered (3MC) states, as well as stabilized triplet metal-to-ligand charge transfer (3MLCT) states, conducive to fine emissive performances, Ru-1, Ru-2, Ru-3, and Ru-4 were synthesized. Compared with the [Ru(terpyridine)2]2+ prototype (0.25 ns), this series of ruthenium(II) terpyridine complexes exhibit lengthened excited state lifetime (43.3 ns for Ru-1, 52.7 ns for Ru-2, 43.6 ns for Ru-3, and 53.4 ns for Ru-4). Interfragment charge transfer analysis illustrates the electron transfer direction of the four complexes, manifesting their intramolecular charge transfer characteristic. When excited, their lowest-lying triplet states are assigned as 3MLCT based on spin-density surface distribution. The singlet excited states and 3MLCT states were thoroughly studied by UV-visual absorption and nanosecond time-resolved transient absorption spectra, respectively. Photoluminescence spectra revealed their weak broadband near-infrared emission at room temperature and red phosphorescence at 77 K. The low molecular weight and the good thermal stability make Ru-1 and Ru-2 suitable for vaporization coating, while the fine solubility in common organic solvents makes Ru-3 and Ru-4 suitable for solution processing. Furthermore, the intrinsic electroneutrality and favorable energy levels endow them with new potential to be applied in the optoelectronic field.