Universität zu Köln

von der Stueck, Rene, Krause, Maren, Bruenink, Dana, Buss, Stefan, Doltsinis, Nikos L., Strassert, Cristian A. and Klein, Axel (2022). Luminescent Pd(II) Complexes with Tridentate C-perpendicular to N perpendicular to N Aryl-pyridine-(benzo)thiazole Ligands. Z. Anorg. Allg. Chem., 648 (1). WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1521-3749

Full text not available from this repository.

Abstract

Cyclometalated Pd(II) complexes generally show inferior luminescence properties compared with their Pt(II) analogues. The established approach employing tridentate C perpendicular to N perpendicular to N cyclometalating ligands has allowed us to create a series of square planar Pd(II) complexes [Pd(C perpendicular to N perpendicular to N )X] from their protoligands HC perpendicular to N perpendicular to N (2-(6-phenylpyridin-2-yl)thiazoles and -benzothiazoles; coligands X=Cl, Br, I) with extensive variations at the C-arene group (phenyl, naphthyl, fluorenyl), the central N-pyridine (pyridine, 4-phenylpyridine, 3,5-di-tert-butyl-4-phenylpyridine), and the peripheral N-thiazole (thiazole, benzothiazole) to probe for structural factors that might enhance efficient luminescence. Long-wavelength bands at 400-500 nm were assigned to transitions into mixed ligand-centred/metal-to-ligand charge transfer (MLCT) states based on time-dependent (TD)DFT calculations. The MLCT contributions are rather low, in agreement with relatively long lifetimes and high photoluminescence quantum yields of up to 0.79 recorded in frozen glassy solvent matrices at 77 K along with emission bands showing pronounced vibrational progressions and peaking at about 520 nm. No photoluminescence was observed at 298 K in solution. Variation of the C perpendicular to N perpendicular to N ligand allowed to shift the experimental absorption energies from about 2.4 to 2.7 eV, in good agreement with the electrochemical band gaps (2.58 to 2.81 eV). The theoretical absorption and emission spectra excellently reproduced the experimental trends.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code von der Stueck, Rene UNSPECIFIED UNSPECIFIED UNSPECIFIED Krause, Maren UNSPECIFIED UNSPECIFIED UNSPECIFIED Bruenink, Dana UNSPECIFIED UNSPECIFIED UNSPECIFIED Buss, Stefan UNSPECIFIED UNSPECIFIED UNSPECIFIED Doltsinis, Nikos L. UNSPECIFIED UNSPECIFIED UNSPECIFIED Strassert, Cristian A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-569832
DOI:	10.1002/zaac.202100278
Journal or Publication Title:	Z. Anorg. Allg. Chem.
Volume:	648
Number:	1
Date:	2022
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1521-3749
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language ELECTROCHEMICAL PROPERTIES; PHOTOPHYSICAL PROPERTIES; PLATINUM(II) COMPLEXES; CYCLOMETALATED PT(II); SPECTROSCOPIC PROPERTIES; PALLADIUM(II) COMPLEXES; EXCITED-STATE; PT-II; EMITTERS; PD Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/56983