title: Impact of the synergistic collaboration of oligothiophene bridges and ruthenium complexes on the optical properties of dumbbell-shaped compounds.
abstract: The linear and non-linear optical properties of a family of dumbbell-shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2'-bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non-linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4, with 3 and 6 thiophene rings, respectively), owing to the presence of the (3)π-π* state of the conjugated bridge below the (3)MLCT-emitting states of the end-capping Ru(II) complexes. In contrast, the compound with the shortest bridge (2, one thiophene ring) shows excellent photophysical features. Non-linear optical experiments showed that the investigated compounds were strong non-linear absorbers in wide energy ranges. Indeed, their non-linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two-photon absorption (TPA) but also noteworthy three-photon-absorption behavior, with a cross-section value of 4×10(-78) cm(6) s(2) at 1450 nm. This characteristic was complemented by the strong excited-state absorption (ESA) that was observed for compounds 3 and 4. As a matter of fact, the overlap between the non-linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical-power-limiting applications.
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, 46980 Paterna, Valencia, Spain. ruben.costa@uv.es
authors.forename: Rubén D
authors.initials: RD
authors.lastname: Costa
authors.forename: Juan
authors.initials: J
authors.lastname: Aragó
authors.forename: Enrique
authors.initials: E
authors.lastname: Ortí
authors.forename: Ted M
authors.initials: TM
authors.lastname: Pappenfus
authors.forename: Kent R
authors.initials: KR
authors.lastname: Mann
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Matczyszyn
authors.forename: Marek
authors.initials: M
authors.lastname: Samoc
authors.forename: José L
authors.initials: JL
authors.lastname: Zafra
authors.forename: Juan T
authors.initials: JT
authors.lastname: López Navarrete
authors.forename: Juan
authors.initials: J
authors.lastname: Casado
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D008024:Ligands; D011789:Quantum Theory; D012428:Ruthenium / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D013816:Thermodynamics; D013876:Thiophenes / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D008024:Ligands; D013876:Thiophenes; D012428:Ruthenium