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