Investigation of Luminescent Triplet States in Tetranuclear Cu$^{I}$ Complexes: Thermochromism and Structural Characterization

To develop new and flexible CuI 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 CuI 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 (3 m/XLCT) and cluster‐centered (3CC) states were obtained and interpreted by comparison with calculated vibrational spectra. The systematic and significant dependence of the bridging halides was analyzed.
Highly luminescent! The synthesis and an in‐depth photophysical characterization of highly luminescent tetranuclear CuI complexes are presented. For these promising candidates for organic light‐emitting diodes, a pronounced luminescence thermochromism with clearly separated emission bands is observed. The corresponding excited state structures are determined by applying temperature‐dependent time‐resolved step‐scan FTIR spectroscopy in combination with DFT calculations.