Authors:	Sikora, Philipp Naumann, Robert Förster, Christoph Heinze, Katja
Title:	Excited state energy landscape of phosphorescent group 14 complexes
Online publication date:	20-Apr-2023
Year of first publication:	2023
Language:	english
Abstract:	Great progress has been achieved on phosphorescent or photoactive complexes of the Earth-abundant transition metals, while examples for phosphorescent heavy main group element complexes are rare, in particular for group 14 complexes in the oxidation state +II. The known compounds often show only weak phosphorescence with fast non-radiative deactivation. The underlying photophysical processes and the nature of the phosphorescent electronic states have remained essentially unexplored. The present combined photophysical and theoretical study on tin(II) and lead(II) complexes E(bpep) with the dianionic tridentate ligand bpep2− (E = Sn, Pb; H2bpep = 2-[1,1-bis(1H-pyrrol-2-yl)ethyl]pyridine) provides unprecedented insight in the excited state energy landscape of tetrel(II) complexes. The tin complex shows green intraligand charge transfer (ILCT) phosphorescence both in solution and in the solid state. In spite of its larger heavy-atom effect, the lead complex only shows very weak red phosphorescence from a strongly distorted ligand-to-metal charge transfer (LMCT) state at low temperatures in the solid state. Detailed (TD-)DFT calculations explain these observations and delineate the major path of non-radiative deactivation via distorted LMCT states. These novel insights provide rational design principles for tetrel(II) complexes with long-lived phosphorescence.
DDC:	540 Chemie 540 Chemistry and allied sciences
Institution:	Johannes Gutenberg-Universität Mainz
Department:	FB 09 Chemie, Pharmazie u. Geowissensch.
Place:	Mainz
ROR:	https://ror.org/023b0x485
DOI:	http://doi.org/10.25358/openscience-8936
Version:	Published version
Publication type:	Zeitschriftenaufsatz
Document type specification:	Scientific article
License:	CC BY-NC
Information on rights of use:	https://creativecommons.org/licenses/by-nc/4.0/
Journal:	Chemical science 14 10
Pages or article number:	2489 2500
Publisher:	RSC
Publisher place:	Cambridge
Issue date:	2023
ISSN:	2041-6539
Publisher DOI:	10.1039/d2sc06984a
Appears in collections:	DFG-491381577-D