Synthesis of cyclometallated platinum complexes with substituted thienylpyridines and detailed characterization of their luminescence properties

Kozhevnikov, Dmitry, Kozhevnikov, Valery, Santoro, Amedeo, Bruce, Duncan, Koenig, Burkhard, Czerwieniec, Rafal, Fischer, Tobias, Zabel, Manfred, Yersin, Hartmut and Ustinova, Maria (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

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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 3ππ* character, which experience only weak spin−orbit couplings to higher lying singlet states.

Item Type:	Article
Subjects:	F100 Chemistry
Department:	Faculties > Health and Life Sciences > Applied Sciences
Depositing User:	EPrint Services
Date Deposited:	25 Feb 2010 14:42
Last Modified:	12 Oct 2019 18:25
URI:	http://nrl.northumbria.ac.uk/id/eprint/2020

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