Tris Diimine Ruthenium Research Articles

π-Expansive Heteroleptic Ruthenium(II) Complexes as Reverse Saturable Absorbers and Photosensitizers for Photodynamic Therapy.

Five heteroleptic tris-diimine ruthenium(II) complexes [RuL(N^N)2](PF6)2 (where L is 3,8-di(benzothiazolylfluorenyl)-1,10-phenanthroline and N^N is 2,2'-bipyridine (bpy) (1), 1,10-phenanthroline (phen) (2), 1,4,8,9-tetraazatriphenylene (tatp) (3), dipyrido[3,2-a:2',3'-c]phenazine (dppz) (4), or benzo[i]dipyrido[3,2-a:2',3'-c]phenazine (dppn) (5), respectively) were synthesized. The influence of π-conjugation of the ancillary ligands (N^N) on the photophysical properties of the complexes was investigated by spectroscopic methods and simulated by density functional theory (DFT) and time-dependent DFT. Their ground-state absorption spectra were characterized by intense absorption bands below 350 nm (ligand L localized 1π,π* transitions) and a featureless band centered at ∼410 nm (intraligand charge transfer (1ILCT)/1π,π* transitions with minor contribution from metal-to-ligand charge transfer (1MLCT) transition). For complexes 4 and 5 with dppz and dppn ligands, respectively, broad but very weak absorption (ε < 800 M-1 cm-1) was present from 600 to 850 nm, likely emanating from the spin-forbidden transitions to the triplet excited states. All five complexes showed red-orange phosphorescence at room temperature in CH2Cl2 solution with decreased lifetimes and emission quantum yields, as the π-conjugation of the ancillary ligands increased. Transient absorption (TA) profiles were probed in acetonitrile solutions at room temperature for all of the complexes. Except for complex 5 (which showed dppn-localized 3π,π* absorption with a long lifetime of 41.2 μs), complexes 1-4 displayed similar TA spectral features but with much shorter triplet lifetimes (1-2 μs). Reverse saturable absorption (RSA) was demonstrated for the complexes at 532 nm using 4.1 ns laser pulses, and the strength of RSA decreased in the order: 2 ≥ 1 ≈ 5 > 3 > 4. Complex 5 is particularly attractive as a broadband reverse saturable absorber due to its wide optical window (430-850 nm) and long-lived triplet lifetime in addition to its strong RSA at 532 nm. Complexes 1-5 were also probed as photosensitizing agents for in vitro photodynamic therapy (PDT). Most of them showed a PDT effect, and 5 emerged as the most potent complex with red light (EC50 = 10 μM) and was highly photoselective for melanoma cells (selectivity factor, SF = 13). Complexes 1-5 were readily taken up by cells and tracked by their intracellular luminescence before and after a light treatment. Diagnostic intracellular luminescence increased with increased π-conjugation of the ancillary N^N ligands despite diminishing cell-free phosphorescence in that order. All of the complexes penetrated the nucleus and caused DNA condensation in cell-free conditions in a concentration-dependent manner, which was not influenced by the identity of N^N ligands. Although the mechanism for photobiological activity was not established, complexes 1-5 were shown to exhibit potential as theranostic agents. Together the RSA and PDT studies indicate that developing new agents with long intrinsic triplet lifetimes, high yields for triplet formation, and broad ground-state absorption to near-infrared (NIR) in tandem is a viable approach to identifying promising agents for these applications.

Visible Light Induced Catalytic Water Reduction without an Electron Relay

Protons from water are reduced by a catalytic system composed of a heteroleptic iridium(III) photosensitizer [Ir(ppy)2(bpy)]+, platinum catalyst, and sacrificial reductant. The hydrogen quantum yield reaches 0.26 in this study, which proceeds via reductive quenching of the excited photosensitizer by triethanolamine. This simplified approach allows the characterization of degradation products that are otherwise obscured in more complex systems. A novel 16-well setup for parallel kinetic analysis of H2 evolution enables high-throughput screening of reaction conditions and quantization of the decaying reaction rate. DFT calculations rationalize the differences between this and previous studies on tris-diimine ruthenium(II) photosensitizers.

Light-Driven Expulsion of the Sterically Hindering Ligand L in Tris-diimine Ruthenium(II) Complexes of the Ru(phen)2(L)2+ Family: A Pronounced Ring Effect

Three new ruthenium(II) complexes have been prepared which contain two 1,10-phenanthroline units and a third sterically hindering chelate. In one case, the hindering ligand is a disubstituted 2,2'-bipyridine (bpy) attached to two very bulky manisyl groups. The two other systems are similar in terms of size of the hindering groups (anisyl substituents) located close to the central metal. The complexes investigated in the Present Report are aimed at providing building blocks of future light-driven molecular machines. The photochemical expulsion of the sterically hindering chelate has thus been studied by UV-vis spectroscopy and 1H NMR. Surprisingly, the manisyl-containing complex turned out to be photochemically inert, indicating that a too bulky group acts as a protecting function versus decomplexation rather than as a destabilizing group. For the two other systems, a pronounced ring effect was observed: whereas the acyclic systems undergo fast photochemical expulsion of the bipy-based ligand, in the cyclic complex, the bipy-incorporating ring is decoordinated about 5 times less efficiently than the acyclic ligand of the previous case. These observations on the strong dependence of the photochemical behavior of the ruthenium(II) complexes on their structural properties are corroborated by X-ray diffraction studies on the three compounds investigated.

Efficient enantiorecognition of ruthenium(II) complexes by silica-bound teicoplanin

A series of chiral tris-diimine ruthenium(II) complexes have been resolved by HPLC on a chiral stationary phase. The stationary phase ( CSP1) was prepared by covalent attachment of the glycopeptide antibiotic teicoplanin to isocyanate activated silica gel. CSP1 selectively retains the enantiomers of [Ru(L) 3] 2+ (L=2,2′-bypyridine (bpy), 1,10-phenanthroline and 4,7-diphenyl-1,10-phenanthroline), with a preference for the Δ isomer. For the mixed-ligand complexes [Ru(bpy) 2pztr] + and [Ru(bpy) 2pytr] + (Hpztr=3-(pyrazin-2-yl)-1,2,4-triazole, Hpytr=3-(pyridin-2-yl)-1,2,4-triazole), where the triazole unit is bound to the metal centre either through the N 2 or the N 4 nitrogen of the ring, CSP1 discriminates both the enantiomers and the regioisomers. Diastereo- and enantioselective association was also observed between CSP1 and the stereoisomers of the dinuclear complex ((Ru(bpy) 2) 2bpt] 3+ (Hbpt=3,5-bis(pyridin-2-yl)-1,2,4-triazole), with differences in binding affinities of 1.4 kJ/mol between the homochiral enantiomers.

A new tris-diimine ruthenium(II) derivative: nucleophilic ring opening of coordinated diazafluorenone

Nucleophilic attack at the carbonyl carbon atom of 4,5-diazafluoren-9-one coordinated to ruthenium(II) causes ring opening resulting in a 3 substituted bipyridine ligand. A similar reaction does not occur with the free ligand. The driving force for the reaction is related to structure changes which occur upon ring opening when 4,5-diazafluoren-9-one is coordinated to ruthenium(II).

Characterization of exciplexes generated by excited tris-diimine—ruthenium(II) complexes and silver(I) ion of ground state

Luminescent bimolecular and termolecular exciplexes of *[Ru(bpy) 3] 2− and *[Ru(phen) 3] 2+ (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) formed by silver ions have been characterized and compared. Formation constants, luminescence lifetime, radiative and non-radiative decay constants were determined at room temperature. Oxidative quenching measurements in the [Ru(bpy) 3] 2−—Ag + system using MV 2+ (MV 2+ = 1,1'-dimethyl-4,4'-bipyridinium) as an electron acceptor resulted in quenching rate constants, (3.1 ± 0.2) × 10 9, (3.1 ± 0.3) × 10 9, (1.6 ± 0.3) × 10 9 and cage escape efficiencies, 0.11 ± 0.01, 0.05 ± 0.01, 0.06 ± 0.01, for *[Ru(bpy) 3] 2+, *[Ru(bpy) 3]Ag 3+ and *[Ru(bpy) 3]Ag 2 4+, respectively. Temperature-dependent luminescence lifetime measurements in aqueous solutions revealed that the exciplex formation causes a considerable change in the deactivation pathways of the excited species. Exciplex formation results in a decrease in the efficiency of the thermally activated decay through MLCT å dd transition and in an increase of the efficiency of deactivation to the ground state via other non radiative processes. The thermodynamic parameters of the exciplex formation have been estimated.