Modulations of a Metal-Ligand Interaction and Photophysical Behaviors by Huckel-Mobius Aromatic Switching

摘要

In organometallic complexes containing pi-conjugated macrocyclic chelate ligands, conformational change significantly affects metal-ligand electronic interactions, hence tuning properties of the complexes. In this regard, we investigated the metal-ligand interactions in hexaphyrin mono-Pd(II) complexes Pd28M and Pd26H, which exhibit a redox-induced switching of Huckel-Mobius aromaticity and subsequent molecular conformation, and their effect on the electronic structure and photophysical behaviors. In Mobius aromatic Pd28M, the weak metal-ligand interaction leads to the pi electronic structure of the hexaphyrin ligand remaining almost intact, which undergoes efficient intersystem crossing (ISC) assisted by the heavy-atom effect of the Pd metal. In Huckel aromatic Pd26H, the significant metal-ligand interaction results in ligand-to-metal charge-transfer (LMCT) in the excited-state dynamics. These contrasting metal-ligand electronic interactions have been revealed by time-resolved electronic and vibrational spectroscopies and time-dependent DFT calculations. This work indicates that the conspicuous modulation of metal-ligand interaction by Huckel-Mobius aromaticity switching is an appealing approach to manipulate molecular properties of metal complexes, further enabling the fine-tuning of metal-ligand interactions and the novel design of functional organometallic materials.