Near-infrared
luminescent materials have recently received considerable
attention for a large number of applications, including in solid-state
lighting, as bioimaging agents, as photovoltaic cells, and in the
telecommunication industry. By adding diverse electron-donating or
withdrawing groups on ancillary ligands based on benzenethiol-phenanthroline,
we synthesized and optoelectronically characterized a series of novel
ionic ruthenium complexes, namely RuS, RuSCl, RuSMe, and RuSNH2, for using in a light-emitting electrochemical cell. The
synthesized complexes are intense red emitters in the range of 584–605
nm in solution, which depends on the substitutions of electron donor/acceptor
moieties on the ancillary ligands. To find a suitable quantum mechanical
approach, benchmark calculations based on time-dependent density functional
theory were carried out on these complexes. Our benchmark revealed
that the M06-L method has results close to those of the experiment.
Furthermore, to gain a deeper insight into electronic transitions,
several excitation processes were investigated at the TD-DFT-SMD-MN12-L/gen
level. The results showed that in the designed complexes, the dominant
transition is between the 4d
Z
2
electron of Ru (particle) and the π* orbitals of the ancillary
ligand (hole). The single-layer devices, including these complexes
along with a Ga/In cathode by a facile deposition method without the
addition of any electron or hole transport layers, were fabricated
and displayed red (678 nm) to near-infrared (701 nm) emission as well
as a decrease of turn-on voltage from 3.85 to 3.10 V. In particular,
adding a methyl group to the ancillary ligand in the complex RuSNH2 increases the external quantum efficiency to 0.55%, one of
the highest observed values in the ruthenium phenanthroline family.
This simple structure of the device lets us develop the practical
applications of light-emitting electrochemical cells based on injection
and screen-printing methods, which are very promising for the vacuum-free
deposition of top electrodes.