The role of zero-field splitting and pi-stacking interaction of different nitrogen-donor ligands on the optical properties of luminescent rhenium tricarbonyl complexes
Abstract
Rhenium tricarbonyl complexes are among the most important classes of coordination compounds in inorganic chemistry. Exploring their luminescent excited states, the lowest singlet (S-1) and lowest triplet (T-1), is an important topic to understand their interesting photophysical behavior and potential applications in organic light-emitting diodes (OLEDs). In this work, a systematic evaluation of the role of zero-field splitting (ZFS) and the geometric arrangement of different nitrogen-donor ligands, including pi-stacking interactions, in five selected rhenium luminescent complexes was performed. The optical properties have been deeply discussed using relativistic quantum mechanics methods and other theoretical approaches. Spin-orbit coupling TDDFT (SOC-TDDFT) calculations showed an excellent prediction of emission properties. The zero-field splitting (ZFS) values were relatively large, verifying the presence of the (MLCT)-M-3 state in the transition character of T1 and efficient spin-orbit coupling (SOC). The introduction of two nitrogen-donor ligands introduced pi-stacking interactions that produced a synergistic effect between the ligands and the metal center, promoting blueshift emissions and higher rate constants for T-1-S-0 transition mediated by SOC.
Más información
Título según WOS: | The role of zero-field splitting and pi-stacking interaction of different nitrogen-donor ligands on the optical properties of luminescent rhenium tricarbonyl complexes |
Título de la Revista: | NEW JOURNAL OF CHEMISTRY |
Volumen: | 45 |
Número: | 25 |
Editorial: | ROYAL SOC CHEMISTRY |
Fecha de publicación: | 2021 |
Página de inicio: | 11192 |
Página final: | 11201 |
DOI: |
10.1039/D1NJ01544C |
Notas: | ISI |