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

Copper and gold cyclic (alkyl)(amino)carbene complexes with sub-microsecond photoemissions: Structure and substituent effects on redox and luminescent properties

Copper and gold halide and pseudo-halide complexes stabilized by methyl-, ethyl- and adamantyl-substituted cyclic (alkyl)(amino)¬carbene (CAAC) ligands are mostly linear monomers in the solid state, without aurophilic Au···Au interactions. (Et2L)CuCl shows the highest photoluminescence quantum yield (PLQY) in the series, 70%. The photoemissions of Me2L and Et2L copper halide complexes show S1 → S0 fluorescence on the ns time scale, in agreement with theory, as well as a minor long-lived emission. Monomeric (Me2L)CuNCS is a white emitter, while dimeric [(Et2L)Cu(µ-NCS)]2 shows intense yellow emission with a PLQY of 49%. The reaction of (AdL)MCl (M = Cu or Au) with phenols ArOH (Ar = Ph, 2,6-F2C6H3, 2,6-Me2C6H3, 3,5-But2C6H3, 2-But-5-MeC6H3, 2-pyridyl), thiophenol, or aromatic amines H2NAr' (Ar' = Ph, 3,5-(CF3)2C6H3, C6F5, 2-py) afforded the corresponding phenolato, thiophenolato and amido complexes. Whereas the emission wavelengths are only marginally affected by the ring substitution pattern, the PL intensities respond sensitively to the presence of substituents in ortho or meta position. In gold aryloxides PL is controlled by steric factors, with strong luminescence in compounds with Au-O-C-C torsion angles <50. Calculations confirm the dependence of oscillator strength on the torsion angle, as well as the inter-ligand charge transfer nature of the emission. The HOMO/LUMO energy levels were estimated based on first reduction and oxidation potentials

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

Secundae Partis Disputationum Quaestionum Illustrium, Ex Logicis, Physicis, Ethicis, Et Metaphysicis ...

SECUNDAE PARTIS DISPUTATIONUM QUAESTIONUM ILLUSTRIUM, EX LOGICIS, PHYSICIS, ETHICIS, ET METAPHYSICIS ... Secundae Partis Disputationum Quaestionum Illustrium, Ex Logicis, Physicis, Ethicis, Et Metaphysicis ... (-) Secundae Partis Disputationum Quaestionum Illustrium, Ex Logicis, Physicis, Ethicis, Et Metaphysicis ... (1) ([1]r) Titelseite ([1]r) Widmung ([1]v) Disputatio Prima ([2]r

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