Krause, Maren, Kourkoulos, Dimitrios ORCID: 0000-0002-0434-4404, Gonzalez-Abradelo, Dario, Meerholz, Klaus, Strassert, Cristian A. and Klein, Axel ORCID: 0000-0003-0093-9619 (2017). Luminescent Pt-II Complexes of Tridentate Cyclometalating 2,5-Bis(aryl)-pyridine Ligands. Eur. J. Inorg. Chem. (44). S. 5215 - 5224. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1099-0682

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Abstract

Bis-cyclometalated Pt-II complexes of dianionic 2,5-bis(aryl)-pyridine ligands (L1-6)(2-), carrying various cyclometalating or pending aryl groups, are synthesised in two steps. The reactions of H2L protoligands with K-2[PtCl4] in acetic acid give the mono-cyclometalated complexes [Pt(HL)Cl](2). Heating these complexes in hot DMSO (dimethyl sulfoxide) yields the double-cyclometalated DMSO complexes [Pt(L1-6)(DMSO)]. The reaction of [Pt(L-4)(DMSO)] with N,N-dimethylimidazolium iodide in the presence of KOtBu as the base gives the carbene complex [Pt(L-4)(Me(2)Imd)]. Detailed photophysical studies reveal the intense orange luminescence of these complexes in CH2Cl2 solution, with quantum yields up to 0.22, and increased quantum yields of up to 1.00 in glassy frozen CH2Cl2/MeOH (1:1) and up to 0.44 in PMMA matrices. Detailed electrochemistry (including spectroelectrochemistry) reveals reversible ligand-based first reductions at -2.1 to -2.3 V, irreversible Pt-centred oxidations at around 0.8 V and electrochemical band gaps of 2.8-3.0 eV. Further reduction waves at very negative potentials interfere with the solvent (THF with traces of water) discharge and can be traced, with UV/Vis spectroelectrochemistry, to Pt-centred reductions for the DMSO complexes and to a second ligand-centred reduction for the Me(2)Imd complex from. The photo/electrochemical properties can be roughly correlated with the ligand pattern and suggest their use in optoelectronic applications.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Krause, MarenUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Kourkoulos, DimitriosUNSPECIFIEDorcid.org/0000-0002-0434-4404UNSPECIFIED
Gonzalez-Abradelo, DarioUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Meerholz, KlausUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Strassert, Cristian A.UNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Klein, AxelUNSPECIFIEDorcid.org/0000-0003-0093-9619UNSPECIFIED
URN: urn:nbn:de:hbz:38-209233
DOI: 10.1002/ejic.201700792
Journal or Publication Title: Eur. J. Inorg. Chem.
Number: 44
Page Range: S. 5215 - 5224
Date: 2017
Publisher: WILEY-V C H VERLAG GMBH
Place of Publication: WEINHEIM
ISSN: 1099-0682
Language: English
Faculty: Faculty of Mathematics and Natural Sciences
Divisions: Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
BOOLEAN-AND-C; PLATINUM(II) COMPLEXES; SPECTROSCOPIC PROPERTIES; CRYSTAL-STRUCTURES; ORGANOPLATINUM(II) COMPLEXES; PHOTOPHYSICAL PROPERTIES; H ACTIVATION; N N; DERIVATIVES; DINUCLEARMultiple languages
Chemistry, Inorganic & NuclearMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/20923

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