Luminescent copper(I) halide and pseudohalide phenanthroline complexes revisited: simple structures, complicated excited state behavior

Dalton Transactions : an International Journal of Inorganic Chemistry
Jörn NitschAndreas Steffen

Abstract

We have synthesized a series of luminescent trigonal [CuX(dtbphen)] (X = I (), Br (), Cl (), CN (), dtbphen = 2,9-di-tert-butylphenanthroline) and tetrahedral [Cu2(μ-I)2(L)2] (L = phenanthroline (), 2,9-dimethylphenanthroline ()) copper diimine complexes. Bearing in mind the chemical simplicity of this class of long-known Cu(i) phenanthroline compounds, it is surprising that they exhibit non-trivial photophysical properties, which have not been fully recognized. They display broad XMLCT absorption between ca. 450-600 nm, and the broad emission between ca. 550-850 nm in the solid state occurring with lifetimes on the μs timescale indicates phosphorescence, although the energetic overlap between excitation and emission suggests thermally activated delayed fluorescence (TADF) from S1. In line with the latter assumption, low temperature measurements of in the solid state show an energetic separation of emission and excitation. However, a counter-intuitive decrease of emission intensity and simultaneous increase of the emission lifetime at low temperatures are observed for , which indicates two triplet states also being involved. Our DFT and TD-DFT calculations show that emission from the lowest excited triplet state T1 is of (3)LMX...Continue Reading

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Citations

Jun 9, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Liju KangCan-Zhong Lu
Jun 24, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Christoph Kreitner, Katja Heinze
Oct 14, 2016·Inorganic Chemistry·Natasha M KhatriSarah L Stoll
Feb 22, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Marian HebenbrockCristian A Strassert
Sep 22, 2018·Physical Chemistry Chemical Physics : PCCP·Yuan-Jun GaoGanglong Cui
Jul 7, 2018·Beilstein Journal of Organic Chemistry·Veronika HladíkováJiří Hanusek
Jun 10, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Shingo MasaharaTomohito Ide

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