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Controlling of Photophysical Behavior of Rhenium(I) Complexes with 2,6-Di(thiazol-2-yl)pyridine-Based Ligands by Pendant π-Conjugated Aryl Groups.

ABSTRACT: The structure-property correlations and control of electronic excited states in transition metal complexes (TMCs) are of high significance for TMC-based functional material development. Within these studies, a series of Re(I) carbonyl complexes with aryl-substituted 2,6-di(thiazol-2-yl)pyridines (Arⁿ-dtpy) was synthesized, and their ground- and excited-state properties were investigated. A number of condensed aromatic rings, which function as the linking mode of the aryl substituent, play a fundamental role in controlling photophysics of the resulting [ReCl(CO)₃(Arⁿ-dtpy-κ²N)]. Photoexcitation of [ReCl(CO)₃(Arⁿ-dtpy-κ²N)] with 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl leads to the population of ³MLCT. The lowest triplet state of Re(I) chromophores bearing 9-anthryl, 2-anthryl, 1-pyrenyl groups is ligand localized. The rhenium(I) complex with appended 1-pyrenyl group features long-lived room temperature emission attributed to the equilibrium between ³MLCT and ³IL/³ILCT. The excited-state dynamics in complexes [ReCl(CO)₃(9-anthryl-dtpy-κ²N)] and [ReCl(CO)₃(2-anthryl-dtpy-κ²N)] is strongly dependent on the electronic coupling between anthracene and {ReCl(CO)₃(dtpy-κ²N)}. Less steric hindrance between the chromophores in [ReCl(CO)₃(2-anthryl-dtpy-κ²N)] is responsible for the faster formation of ³IL/³ILCT and larger contribution of ³ILCT_anthracene_→_dtpy in relation to the isomeric complex [ReCl(CO)₃(9-anthryl-dtpy-κ²N)]. In agreement with stronger electronic communication between the aryl and Re(I) coordination centre, [ReCl(CO)₃(2-anthryl-dtpy-κ²N)] displays room-temperature emission contributed to by ³MLCT and ³IL_anthracene/³ILCT_anthracene_→_dtpy phosphorescence. The latter presents rarely observed phenomena in luminescent metal complexes.

SUBMITTER: Maron AM

PROVIDER: S-EPMC9569785 | biostudies-literature | 2022 Sep

REPOSITORIES: biostudies-literature

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Controlling of Photophysical Behavior of Rhenium(I) Complexes with 2,6-Di(thiazol-2-yl)pyridine-Based Ligands by Pendant π-Conjugated Aryl Groups.

Maroń Anna M AM Palion-Gazda Joanna J Szłapa-Kula Agata A Schab-Balcerzak Ewa E Siwy Mariola M Sulowska Karolina K Maćkowski Sebastian S Machura Barbara B

International journal of molecular sciences 20220920 19

The structure-property correlations and control of electronic excited states in transition metal complexes (TMCs) are of high significance for TMC-based functional material development. Within these studies, a series of Re(I) carbonyl complexes with aryl-substituted 2,6-di(thiazol-2-yl)pyridines (Ar<sup>n</sup>-dtpy) was synthesized, and their ground- and excited-state properties were investigated. A number of condensed aromatic rings, which function as the linking mode of the aryl substituent, ...[more]

PMID: 36232327

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Project description:The donor-acceptor-π-conjugated (D-π-)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2 with two (diphenylamino)carbazole thiophene units as D (electron-donating group)-π (π-conjugated bridge) moiety and a pyridine, pyrazine or triazine ring as electron-withdrawing group (electron-accepting group, A) have been designed and synthesized. The photophysical and electrochemical properties of the three dyes were investigated by photoabsorption and fluorescence spectroscopy, Lippert-Mataga plots, cyclic voltammetry and density functional theory calculations. The photoabsorption maximum (λmax,abs) and the fluorescence maximum (λmax,fl) for the intramolecular charge-transfer characteristic band of the (D-π-)2A fluorescent dyes show bathochromic shifts in the order of OUY-2 < OUK-2 < OUJ-2. Moreover, the photoabsorption bands of the (D-π-)2A fluorescent dyes are nearly independent of solvent polarity, while the fluorescence bands showed bathochromic shifts with increasing solvent polarity (i.e., positive fluorescence solvatochromism). The Lippert-Mataga plots for OUY-2, OUK-2 and OUJ-2 indicate that the Δμ (= μe - μg) value, which is the difference in the dipole moment of the dye between the excited (μe) and the ground (μg) states, increases in the order of OUY-2 < OUK-2 < OUJ-2. Therefore, the fact explains our findings that OUJ-2 shows large bathochromic shifts of the fluorescence maxima in polar solvents, as well as the Stokes shift values of OUJ-2 in polar solvents are much larger than those in nonpolar solvents. The cyclic voltammetry of OUY-2, OUK-2 and OUJ-2 demonstrated that there is little difference in the HOMO energy level among the three dyes, but the LUMO energy levels decrease in the order of OUY-2 > OUK-2 > OUJ-2. Consequently, this work reveals that for the (D-π-)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2 the bathochromic shifts of λmax,abs and λmax,fl and the lowering of the LUMO energy level are dependent on the electron-withdrawing ability of the azine ring, which increases in the order of OUY-2 < OUK-2 < OUJ-2.

Dataset Information

Controlling of Photophysical Behavior of Rhenium(I) Complexes with 2,6-Di(thiazol-2-yl)pyridine-Based Ligands by Pendant π-Conjugated Aryl Groups.

Publications

Controlling of Photophysical Behavior of Rhenium(I) Complexes with 2,6-Di(thiazol-2-yl)pyridine-Based Ligands by Pendant π-Conjugated Aryl Groups.

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