The synthesis and behavior in water of a set of various cis(Cl,Cl)-[R-tpyRuCl2(NO)](PF6) and trans(Cl,Cl)-[R-tpyRuCl2(NO)](PF6) (R = fluorenyl, phenyl, thiophenyl; tpy = 2,2′:6′,2′′-terpyridine) complexes are presented.

One monometallic and three bimetallic ruthenium nitrosyl (RuNO) complexes are presented and fully characterized in reference to a parent monometallic complex of formula [FTRu(bpy)(NO)] 3 + , where FT is a fluorenyl-substituted terpyridine ligand, and bpy the 2,2'-bipyridine. These new complexes are built with the new ligands FFT, TFT, TFFT, and TF-CC-TF (where an alkyne C�C group is inserted between two fluorenes). The crystal structures of the bis-RuNO 2 and bis-RuNO complexes built from the TFT ligand are presented. The evolution of the spectroscopic features (intensities and energies) along the series, at one-photon absorption (OPA) correlates well with the TD-DFT computations. A spectacular effect is observed at two-photon absorption (TPA) with a large enhancement of the molecular cross-section (σ TPA ), in the bimetallic species. In the best case, σ TPA is equal to 1523 � 98 GM at 700 nm, in the therapeutic window of transparency of biological tissues. All compounds are capable of releasing NO * under irradiation, which leads to promising applications in TPA-based drug delivery.

Since the discovery of the numerous physiological roles exhibited by nitric oxide (NO), ruthenium nitrosyl (RuNO) complexes have been regarded as one of most promising NO donors, stable, well tolerated...