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Tuning Optical Properties of Re(I) Carbonyl Complexes by Modifying Push–Pull Ligands Structure
journal contribution
posted on 2019-10-07, 19:51 authored by Tomasz Klemens, Anna Świtlicka, Agata Szlapa-Kula, Łukasz Łapok, Magdalena Obłoza, Mariola Siwy, Marcin Szalkowski, Sebastian Maćkowski, Marcin Libera, Ewa Schab-Balcerzak, Barbara MachuraIn this work, the
structure–property relationship was investigated
for a series of Re(I) carbonyls [ReCl(CO)3(R-terpy-κ2N)], [ReCl(CO)3(R-dtpy-κ2N)], and [ReCl(CO)3(R-dppy-κ2N)]. The studied compounds bear 2,2′:6′,2″-terpyridines
(R-terpy), 2,6-di(thiazol-2-yl)pyridines (R-dtpy), and 2,6-di(pyrazin-2-yl)pyridines (R-dppy) 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 terpy 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)3(R-terpy-κ2N)] in relation
to those of Re(I) carbonyls bearing dtpy- and dppy-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.
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terpy skeletonRedtpyTuning Optical Propertiesdppytriimine skeletonreduction potentialsLUMOintraligand charge-transferlayer diodesphenylene linkageILCTReClelectron-donating cyclicDSCcarbonyldensity-functional theoryhole-transport propertiesexcited-state propertiesDFTemission spectroscopypyridine ringamine substituentsamine donor-κ
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