Origin of a counterintuitive yellow light-emitting electrochemical cell based on a blue-emitting heteroleptic copper() complex

This work provides the synthesis, structural characterization, electrochemical and photophysical features, as well as the application in light-emitting electrochemical cells (LECs) of a novel heteroleptic copper( i ) complex - [Cu(impy)(POP)][PF 6 ], where impy is 3-(2-methoxyphenyl)-1-(pyridine-2-y...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry 2016-01, Vol.45 (21), p.8984-8993
Hauptverfasser: Weber, Michael D, Garino, Claudio, Volpi, Giorgio, Casamassa, Enrico, Milanesio, Marco, Barolo, Claudia, Costa, Rubén D
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Sprache:eng
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Zusammenfassung:This work provides the synthesis, structural characterization, electrochemical and photophysical features, as well as the application in light-emitting electrochemical cells (LECs) of a novel heteroleptic copper( i ) complex - [Cu(impy)(POP)][PF 6 ], where impy is 3-(2-methoxyphenyl)-1-(pyridine-2-yl)imidazo[1,5- a ]pyridine and POP is bis{2-(diphenylphosphanyl)phenyl}ether. This compound shows blue photoluminescence (PL, λ = 450 nm) in solution and solid-state and excellent redox stability. Despite these excellent features, the electroluminescence (EL) response is located at ∼550 nm. Although the EL spectrum of LECs is typically red-shifted compared to the PL of the electroluminescent material, a shift of ca . 100 nm represents the largest one reported in LECs. To date, the large shift phenomena have been attributed to (i) a change in the nature of the lowest emitting state due to a concentration effect of the films, (ii) a reversible substitution of the ligands due to the weak coordination to the Cu( i ), and (iii) a change in the distribution of the excited states due to polarization effects. After having discarded these along with others like the irreversible degradation of the emitter during device fabrication and/or under operation conditions, driving conditions, active layer composition, and changes in the excited states under different external electrical stimuli, we attribute the origin of this unexpected shift to a lack of a thermally activated delayed fluorescence (TADF) process due to the solely ligand-centered character of the excited states. As such, the lack of a charge transfer character in the excited states leads to a blue-fluorescence and yellow-phosphorescence photo- and electro-responses, respectively. This corroborates recent studies focused on the design of TADF for heteroleptic copper( i ) complexes. Overall, this work is a clear insight into the design of new copper( i ) complexes towards the preparation of blue LECs, which are still unexplored. A new copper( i ) complex, which lacks of charge transfer character in the excited state, features a blue fluorescence and yellow phosphorescence photo- and electro-responses, respectively.
ISSN:1477-9226
1477-9234
DOI:10.1039/c6dt00970k