Cu(I)-Komplexe mit Tripod-Liganden – Emitter für den roten bis blauen Farbbereich

Mit der Verwendung von Tripod-Liganden, die das Cu(I)-Zentrum wie ein Skorpionat-Ligand dreizähnig koordinieren, ist in dieser Doktorarbeit ein neues Konzept verfolgt worden, um Cu(I)-Komplexe rigider zu machen. Da solche Cu(I)-Tripod-Komplexe erst unzureichend auf ihre photophysikalischen Eigenschaften untersucht worden sind, sind in dieser Doktorarbeit mit Hilfe von quantenchemischen Rechnungen sowie photophysikalischen Messungen die Grundlagen dieser neuen Emitter-Klasse erforscht worden

Cu(I)-Komplexe mit Tripod-Liganden – Emitter für den roten bis blauen Farbbereich

Mit der Verwendung von Tripod-Liganden, die das Cu(I)-Zentrum wie ein Skorpionat-Ligand dreizähnig koordinieren, ist in dieser Doktorarbeit ein neues Konzept verfolgt worden, um Cu(I)-Komplexe rigider zu machen. Da solche Cu(I)-Tripod-Komplexe erst unzureichend auf ihre photophysikalischen Eigenschaften untersucht worden sind, sind in dieser Doktorarbeit mit Hilfe von quantenchemischen Rechnungen sowie photophysikalischen Messungen die Grundlagen dieser neuen Emitter-Klasse erforscht worden

A new class of deep-blue emitting Cu(I) compounds – effects of counter ions on the emission behavior

Three deep blue emitting Cu(I) compounds, [Cu(PPh3)tpym]PF6, [Cu(PPh3)tpym]BF4, and [Cu(PPh3)tpym]BPh4 (tpym = tris(2-pyridyl)methane, PPh3 = triphenylphosphine) featuring the tripodally coordinating tpym and the monodentate PPh3 ligands were studied with regard to their structural and photophysical properties. The compounds only differ in their respective counter ions which have a strong impact on the emission properties of the powder samples. For example, the emission quantum yield can be significantly increased for the neat material from less than 10% to more than 40% by exchanging BPh4− with PF6−. These effects can be linked to different molecular packings which depend on the counter ion. In agreement with these results, it was found that the emission properties also strongly depend on the surrounding matrix environment which was elucidated by investigating photophysical properties of the compounds as powders, doped into a polymer matrix, and dissolved in a fluid solution, respectively. The observed differences in the emission behavior can be explained by different and pronounced distortions that occur in the excited state. These distortions are also displayed by density functional theory (DFT) calculations

A new class of luminescent Cu(I) complexes with tripodal ligands – TADF emitters for the yellow to red color range

A new class of emissive and neutral Cu(I) compounds with tripodal ligands is presented. The complexes were characterized chemically, computationally, and photophysically. Under ambient conditions, the powders of the compounds exhibit yellow to red emission with quantum yields ranging from about 5% to 35%. The emission represents a thermally activated delayed fluorescence (TADF) combined with a short-lived phosphorescence which represents a rare situation and is a consequence of high spin–orbit coupling (SOC). In the series of the investigated compounds the non-radiative rates increase with decreasing emission energy according to the energy gap law while the radiative rate is almost constant. Furthermore, a well-fit linear dependence between the experimental emission energies and the transition energies calculated by DFT and TD-DFT methods could be established, thus supporting the applicability of these computational methods also to Cu(I) complexes