Universität zu Köln

Friedel, Joshua ORCID: 0000-0001-6215-7271, Krause, Maren, Jordan, Rose ORCID: 0000-0003-0764-1639, Maisuls, Ivan, Bruenink, Dana, Schwab, Dominik, Doltsinis, Nikos L., Strassert, Cristian A. and Klein, Axel ORCID: 0000-0003-0093-9619 (2022). Triplet Emitting C boolean AND N boolean AND C Cyclometalated Dibenzo[c,h]Acridine Pt(II) Complexes. Molecules, 27 (22). BASEL: MDPI. ISSN 1420-3049

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Abstract

In a series of Pt(II) complexes [Pt(dba)(L)] containing the very rigid, dianionic, bis-cyclometalating, tridentate C boolean AND N boolean AND C2- heterocyclic ligand dba(2-) (H(2)dba = dibenzo[c,h]acridine), the coligand (ancillary ligand) L = dmso, PPh3, CNtBu and Me(2)Imd (N,N'-dimethylimidazolydene) was varied in order to improve its luminescence properties. Beginning with the previously reported dmso complex, we synthesized the PPh3, CNtBu and Me(2)Imd derivatives and characterized them by elemental analysis, H-1 (and P-31) NMR spectroscopy and MS. Cyclic voltammetry showed partially reversible reduction waves ranging between -1.89 and -2.10 V and increasing along the series Me(2)Imd < dmso approximate to PPh3 < CNtBu. With irreversible oxidation waves ranging between 0.55 (L = Me(2)Imd) and 1.00 V (dmso), the electrochemical gaps range between 2.65 and 2.91 eV while increasing along the series Me(2)Imd < CNtBu < PPh3 < dmso. All four complexes show in part vibrationally structured long-wavelength absorption bands peaking at around 530 nm. TD-DFT calculated spectra agree quite well with the experimental spectra, with only a slight redshift. The photoluminescence spectra of all four compounds are very similar. In fluid solution at 298 K, they show broad, only partially structured bands, with maxima at around 590 nm, while in frozen glassy matrices at 77 K, slightly blue-shifted (similar to 580 nm) bands with clear vibronic progressions were found. The photoluminescence quantum yields phi(L) ranged between 0.04 and 0.24, at 298 K, and between 0.80 and 0.90 at 77 K. The lifetimes tau at 298 K ranged between 60 and 14040 ns in Ar-purged solutions and increased from 17 to 43 mu s at 77 K. The TD-DFT calculated emission spectra are in excellent agreement with the experimental findings. In terms of high phi(L) and long tau, the dmso and PPh3 complexes outperform the CNtBu and Me(2)Imd derivatives. This is remarkable in view of the higher ligand strength of Me(2)Imd, compared with all other coligands, as concluded from the electrochemical data.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Friedel, Joshua UNSPECIFIED orcid.org/0000-0001-6215-7271 UNSPECIFIED Krause, Maren UNSPECIFIED UNSPECIFIED UNSPECIFIED Jordan, Rose UNSPECIFIED orcid.org/0000-0003-0764-1639 UNSPECIFIED Maisuls, Ivan UNSPECIFIED UNSPECIFIED UNSPECIFIED Bruenink, Dana UNSPECIFIED UNSPECIFIED UNSPECIFIED Schwab, Dominik UNSPECIFIED UNSPECIFIED UNSPECIFIED Doltsinis, Nikos L. UNSPECIFIED UNSPECIFIED UNSPECIFIED Strassert, Cristian A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-667059
DOI:	10.3390/molecules27228054
Journal or Publication Title:	Molecules
Volume:	27
Number:	22
Date:	2022
Publisher:	MDPI
Place of Publication:	BASEL
ISSN:	1420-3049
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language LUMINESCENT METAL-COMPLEXES; PLATINUM(II) COMPLEXES; ORGANOPLATINUM(II) COMPLEXES; SPECTROSCOPIC PROPERTIES; PHOTOPHYSICAL PROPERTIES; PT-II; LIGANDS; EMISSION; DYNAMICS; AGGREGATION Multiple languages Biochemistry & Molecular Biology; Chemistry, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/66705