Universität zu Köln

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:	Creators Email ORCID ORCID Put Code Krause, Maren UNSPECIFIED UNSPECIFIED UNSPECIFIED Kourkoulos, Dimitrios UNSPECIFIED orcid.org/0000-0002-0434-4404 UNSPECIFIED Gonzalez-Abradelo, Dario UNSPECIFIED UNSPECIFIED UNSPECIFIED Meerholz, Klaus UNSPECIFIED UNSPECIFIED UNSPECIFIED Strassert, Cristian A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
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:	Keywords Language BOOLEAN-AND-C; PLATINUM(II) COMPLEXES; SPECTROSCOPIC PROPERTIES; CRYSTAL-STRUCTURES; ORGANOPLATINUM(II) COMPLEXES; PHOTOPHYSICAL PROPERTIES; H ACTIVATION; N N; DERIVATIVES; DINUCLEAR Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/20923