Tuning Optical Properties of Re(I) Carbonyl Complexes
by Modifying Push–Pull Ligands Structure
Tomasz Klemens
Anna Świtlicka
Agata Szlapa-Kula
Łukasz Łapok
Magdalena Obłoza
Mariola Siwy
Marcin Szalkowski
Sebastian Maćkowski
Marcin Libera
Ewa Schab-Balcerzak
Barbara Machura
10.1021/acs.organomet.9b00517.s001
https://acs.figshare.com/articles/journal_contribution/Tuning_Optical_Properties_of_Re_I_Carbonyl_Complexes_by_Modifying_Push_Pull_Ligands_Structure/9946994
In this work, the
structure–property relationship was investigated
for a series of Re(I) carbonyls [ReCl(CO)<sub>3</sub>(R-<i>terpy</i>-κ<sup>2</sup>N)], [ReCl(CO)<sub>3</sub>(R-<i>dtpy</i>-κ<sup>2</sup>N)], and [ReCl(CO)<sub>3</sub>(R-<i>dppy</i>-κ<sup>2</sup>N)]. The studied compounds bear 2,2′:6′,2″-terpyridines
(R-<i>terpy</i>), 2,6-di(thiazol-2-yl)pyridines (R-<i>dtpy</i>), and 2,6-di(pyrazin-2-yl)pyridines (R-<i>dppy</i>) functionalized with strongly electron-donating cyclic (piperidine
and morpholine) and acyclic (dimethylamine, diphenylamine) amine donor
attached to the central pyridine ring of the triimine skeleton via
phenylene linkage. Their thermal properties were evaluated using DSC.
The ground- and excited-state properties of these systems were elucidated
with electrochemistry, absorption and emission spectroscopy, and density-functional
theory (DFT)-based calculations. The <i>terpy</i> skeleton
was found to efficiently stabilize the LUMO orbital, as manifested
by the most negative reduction potentials for Re(I) terpyridine complexes
and significant blue-shift of the absorption and emission of [ReCl(CO)<sub>3</sub>(R-<i>terpy</i>-κ<sup>2</sup>N)] in relation
to those of Re(I) carbonyls bearing <i>dtpy</i>- and <i>dppy</i>-based ligands. Substitution of the triimines with amine
substituents resulted in participation of intraligand charge-transfer
(ILCT) transitions, and it was found to be beneficial for hole-transport
properties of the Re(I) carbonyls. The constructed nondoped and doped
single layer diodes based on Re(I) complexes emitted red light with
various intensity.
2019-10-07 19:51:30
terpy skeleton
Re
dtpy
Tuning Optical Properties
dppy
triimine skeleton
reduction potentials
LUMO
intraligand charge-transfer
layer diodes
phenylene linkage
ILCT
ReCl
electron-donating cyclic
DSC
carbonyl
density-functional theory
hole-transport properties
excited-state properties
DFT
emission spectroscopy
pyridine ring
amine substituents
amine donor
-κ