Investigation of Luminescent Triplet States in Tetranuclear Cu-I Complexes : Thermochromism and Structural Characterization

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Boden , P , Di Martino-Fumo , P , Busch , J M , Rehak , F R , Steiger , S , Fuhr , O , Nieger , M , Volz , D , Klopper , W , Bräse , S & Gerhards , M 2021 , ' Investigation of Luminescent Triplet States in Tetranuclear Cu-I Complexes : Thermochromism and Structural Characterization ' , Chemistry: A European Journal , vol. 27 , no. 17 , pp. 5439-5452 . https://doi.org/10.1002/chem.202004539

Title: Investigation of Luminescent Triplet States in Tetranuclear Cu-I Complexes : Thermochromism and Structural Characterization
Author: Boden, Pit; Di Martino-Fumo, Patrick; Busch, Jasmin M.; Rehak, Florian R.; Steiger, Sophie; Fuhr, Oliver; Nieger, Martin; Volz, Daniel; Klopper, Willem; Bräse, Stefan; Gerhards, Markus
Contributor: University of Helsinki, Department of Chemistry
Date: 2021-03-22
Language: eng
Number of pages: 14
Belongs to series: Chemistry: A European Journal
ISSN: 0947-6539
URI: http://hdl.handle.net/10138/331672
Abstract: To develop new and flexible Cu-I containing luminescent substances, we extend our previous investigations on two metal-centered species to four metal-centered complexes. These complexes could be a basis for designing new organic light-emitting diode (OLED) relevant species. Both the synthesis and in-depth spectroscopic analysis, combined with high-level theoretical calculations are presented on a series of tetranuclear Cu-I complexes with a halide containing Cu4X4 core (X=iodide, bromide or chloride) and two 2-(diphenylphosphino)pyridine bridging ligands with a methyl group in para (4-Me) or ortho (6-Me) position of the pyridine ring. The structure of the electronic ground state is characterized by X-ray diffraction, NMR, and IR spectroscopy with the support of theoretical calculations. In contrast to the para system, the complexes with ortho-substituted bridging ligands show a remarkable and reversible temperature-dependent dual phosphorescence. Here, we combine for the first time the luminescence thermochromism with time-resolved FTIR spectroscopy. Thus, we receive experimental data on the structures of the two triplet states involved in the luminescence thermochromism. The transient IR spectra of the underlying triplet metal/halide-to-ligand charge transfer (M-3/XLCT) and cluster-centered ((CC)-C-3) states were obtained and interpreted by comparison with calculated vibrational spectra. The systematic and significant dependence of the bridging halides was analyzed.
Subject: Cu-I complexes
FTIR spectroscopy
luminescence
theoretical calculations
X-ray diffraction
COPPER-IODIDE CLUSTERS
FLUORESCENCE THERMOCHROMISM
EXCITED-STATE
EMISSION
PHOSPHORESCENCE
SPECTROSCOPY
DINUCLEAR
LIGANDS
BLUE
116 Chemical sciences
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