Synthesis of Cyclometallated Platinum Complexes with Substituted Thienylpyridines and Detailed Characterization of Their Luminescence Properties

Kozhevnikov, Dmitry N. and Kozhevnikov, Valery N. and Ustinova, Maria M. and Santoro, Amedeo and Bruce, Duncan W. and Koenig, Burkhard and Czerwieniec, Rafal and Fischer, Tobias and Zabel, Manfred and Yersin, Hartmut (2009) Synthesis of Cyclometallated Platinum Complexes with Substituted Thienylpyridines and Detailed Characterization of Their Luminescence Properties. INORGANIC CHEMISTRY, 48 (9). pp. 4179-4189. ISSN 0020-1669, 1520-510X

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Abstract

Synthesis of various derivatives of 2-(2-thienyl)pyridine via substituted 3-thienyl-1,2,4-triazines is reported. The final step of the synthesis is a transformation of the triazine ring to pyridine in an aza-Diels-Alder-type reaction. The resulting 5-aryl-2-(2-thienyl)pyridines (HL1-HL4) and 5-aryl-2-(2-thienyl)cyclopenteno[c]pyridines (HL5-HL8) (with aryl = phenyl, 4-methoxyphenyl, 2-naphtyl, and 2-thienyl) were used as cyclometallating ligands to prepare a series of eight luminescent platinum complexes of the type [Pt(L)(acac)] (L = cyclometallating ligand, acac = acetylacetonato). X-ray single crystal structures of three complexes of that series, [Pt(L5)(acac)] = [Pt(5-phenyl-2-(2-thienyl)cyclopenteno[c]pyridine)(acac)], [Pt(L6)(acac)] = [Pt(5-(4-methoxy)-2-(2-thienyl)cyclopenteno[c]pyridine)(acac)], and [Pt(L7)(acac)] = [Pt(5-(2-naphtyl)-2-(2-thienyl) cyclopenteno[c]pyridine)(acac)] were determined. Photoluminescence and electronic absorption spectra of the new [Pt(L)(acac)] complexes are reported. For two representative compounds of that series, [Pt(L4)(acac)] and [Pt(L5)(acac)], a detailed photophysical characterization based on highly resolved emission and excitation spectra, as well as on emission decay properties, was carried out. The studies down to low temperature (T = 1.2 K) and up to high magnetic fields (B = 10 T) allowed us to characterize the three individual substates of the emitting triplet state. In particular, it is shown that the lowest triplet states of [Pt(L4)(acac)] and [Pt(L5)(acac)] are largely ligand-centered (LC) of (3)pi-pi*character, which experience only weak spin-orbit couplings to higher lying singlet states.

Item Type: Article
Uncontrolled Keywords: SIMPLE LEGO SYSTEM; DEMAND DIELS-ALDER; IRIDIUM(III) DIIMINE COMPLEXES; DETECTED MAGNETIC-RESONANCE; INTRALIGAND CHARGE-TRANSFER; SENSITIZED SOLAR-CELLS; ONE-POT SYNTHESIS; ENERGY-GAP LAW; PHOTOPHYSICAL PROPERTIES; HIGH-RESOLUTION;
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König
Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry) > Prof. Dr. Hartmut Yersin
Depositing User: Dr. Gernot Deinzer
Date Deposited: 15 Sep 2020 11:51
Last Modified: 15 Sep 2020 11:51
URI: https://pred.uni-regensburg.de/id/eprint/28984

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