Mono- and Diruthenium, Symmetrical and Unsymmetrical Complexes Bridged by Pyrene Derivatives: Experimental and Theoretical Studies.

New mono- and diruthenium, symmetrical and unsymmetrical complexes, bridged by a new cyclometalating 1,3,6,8-tetra(4-substituted-2-pyridyl)pyrene derivative containing the solubilizing group 2,2-dimethylpropyloxy, with the terminal 4′-phenyl-2,2′:6′,2′′-terpyridine ligands containing diethylamine and a 2-ethynyl-9,9-dioctylfluorene moiety, were synthesized and thoroughly characterized. Thermal studies show that the obtained complexes retain high thermal stability. Spectroscopic studies show the metal-to-ligand charge-transfer excitation. Further, electrochemical studies show delocalization of the electronic charge (mixed valance). In addition, density functional theory and time-dependent density functional theory calculations have provided more detail about the structural properties and a deeper understanding of the experimental results. All of the obtained results show the considerable differences between the mono- and diruthenium and symmetrical and unsymmetrical complexes. [ABSTRACT FROM AUTHOR]