Complexes of the Ruthenium(II)-2,2':6',2''-terpyridine Family. Effect of Electron-Accepting and -Donating Substituents on the Photophysical and Electrochemical Properties

Maestri, Matteo; Armaroli, Nicola; Balzani, Vincenzo; Constable, Edwin C.; Thompson, A.

doi:10.1021/ic00114a039

Cited by 451 publications

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“…Usually, delocalisation of the emitting state is used to increase the lifetime of terpy based excited states [4][5][6][7]. In our approach we have raised the deactivating 3 MC state instead.…”

Section: Discussionmentioning

confidence: 99%

“…2 limitation to the application of this complex as photosensitiser. Improvement of the photophysical properties of terpy-based Ru(II) complexes is therefore currently the object of intensive studies [4][5][6][7][8]. As a contribution to these studies, we wish to report the new [RuL(terpy)] mononuclear complex, where H 2 L is 2,6-bis(1,2,4-triazol-3-yl)pyridine, which exhibits a remarkable 300-fold increase of the emission lifetime when compared with the parent compound [Ru(terpy) 2 ] 2+ ;…”

Section: Introductionmentioning

confidence: 99%

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A new luminescent Ru(terpy) complex incorporating a 1,2,4-triazole based σ-donor ligand

Duati

Fanni

Vos

2000

Inorganic Chemistry Communications

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The mononuclear compound [Ru(terpy)L] , where H 2 L is 2,6-bis(1,2,4-triazol-3-yl)pyridine, shows an emission lifetime of 65 ns, about 300 times longer than that observed for the parent [Ru(terpy) 3 ] 2+ complex.Keywords: Ruthenium; terpyridine; emission lifetime; 1,2,4-triazole. 1.IntroductionRuthenium polypyridine complexes are widely used as photosensitisers in covalently linked multicomponent systems. Their photophysical properties make them ideal candidates as building blocks for the design of supramolecular species performing complex light induced functions [1].The polypyridyl ligands employed are mainly derivatives or analogues of the bidentate 2,2'-bipyridine or derivatives or analogues of the tridentate 2,6,2',2"-terpyridine (terpy) [1][2][3]. Tridentate terpyridine-type ligands are ideal from a geometrical point of view as they can form achiral complexes for which the C 2v symmetry is not affected by substitution in the 4 position of the terpy ligands. Furthermore, the "rod-like" geometry of these complexes offers the best spatial arrangement for the synthesis of triads or molecular wires. However, the very short excited-state lifetime and weak luminescence intensity of [Ru(terpy) 2 ] 2+ at room temperature, represent a severe . 2 limitation to the application of this complex as photosensitiser. Improvement of the photophysical properties of terpy-based Ru(II) complexes is therefore currently the object of intensive studies [4][5][6][7][8]. As a contribution to these studies, we wish to report the new [RuL(terpy)] mononuclear complex, where H 2 L is 2,6-bis(1,2,4-triazol-3-yl)pyridine, which exhibits a remarkable 300-fold increase of the emission lifetime when compared with the parent compound [Ru(terpy) 2 ] 2+ ; 2.Experimental2,6-bis(1,2,4-triazol-3-yl)pyridine was synthesised, in high yield, following the literature pathway [9,10] for similar compounds.The Ru(terpy) complex was obtained by heating [Ru(terpy)]Cl 3 and a stoichiometric amount of the ligand H 2 L in water containing a slight molar excess of NaOH and few drops of N-ethylmorpholine. The reaction mixture was refluxed for two hours; the dark green solution was concentrated, acidified to pH 3 with HCl and an excess of NH 4 PF 6 was added. Purification by column chromatography on alumina (acetonitrile/methanol 50:50) gave a 30% yield.In agreement with literature [11,12], three different isomers were found [Scheme 1]. Isomers A ( 10 %)and B ( 60 %) were eluted from a neutral alumina column using acetonitrile followed by the elution of the isomer C ( 30 %) using methanol. The identification of the three isomers is based on the chemical shift of the triazole proton in the NMR Since isomer C is most easily purified all further studies were carried out using this species, both A and B yield however very similar results. Elemental analysis suggests that a mixture of monoprotonated /deprotonated (80:20) Results and discussionThe UV-Vis absorption spectrum of the complex [Ru(terpy)L], isomer C, in basic ethanol shows an intense metal-to-liga...

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A new luminescent Ru(terpy) complex incorporating a 1,2,4-triazole based σ-donor ligand

Duati

Fanni

Vos

2000

Inorganic Chemistry Communications

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“…On the other hand, for complex 2, we took into account the large body of research that indicated that tridentate polypyridyl ligands generally lead to broad absorption across the visible spectrum and perform inherently well in DSSC. 57,[61][62][63][64] Also in this case, relatively simple ligands were used, with only one carboxylic acid functionality present. Herein we report the synthesis and characterization of two novel Ru(II) polypyridyl PS (1 and 2, Fig.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, and Biological Evaluation of New Ru(II) Polypyridyl Photosensitizers for Photodynamic Therapy

et al. 2014

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Two Ru(II) polypyridyl complexes, Ru(DIP)2(bdt) (1) and [Ru(dqpCO2Me)(ptpy)](2+) (2) (DIP = 4,7-diphenyl-1,10-phenanthroline, bdt = 1,2-benzenedithiolate, dqpCO2Me = 4-methylcarboxy-2,6-di(quinolin-8-yl)pyridine), ptpy = 4'-phenyl-2,2':6',2 -terpyridine) have been investigated as photosensitizers (PSs) for photodynamic therapy (PDT). In our experimental settings, the phototoxicity and phototoxic index (PI) of 2 (IC50(light): 25.3 M, 420 nm, 6.95 J/cm(2); PI >4) and particularly of 1 (IC50(light): 0.62 M, 420 nm, 6.95 J/cm(2); PI: 80) are considerably superior compared to the two clinically approved PSs porfimer sodium and 5-aminolevulinic acid. Cellular uptake and distribution of these complexes was investigated by confocal microscopy (1) and by inductively coupled plasma mass spectrometry (1 and 2). Their phototoxicity was also determined against the Gram-(+) Staphylococcus aureus and Gram-(-) Escherichia coli for potential antimicrobial PDT (aPDT) applications. Both complexes showed significant aPDT activity (420 nm, 8 J/cm(2)) against Gram-(+) (S. aureus; >6 log10 CFU reduction) and, for 2, also against Gram-(-) E. coli (>4 log10 CFU reduction). Two Ru(II) polypyridyl complexes, Ru(DIP)2(bdt) (1) and [Ru(dqpCO2Me)(ptpy)] 2+ (2) (DIP = 4,7-diphenyl-1,10-phenanthroline; bdt = 1,2-benzenedithiolate; dqpCO2Me = 4-methylcarboxy-2,6-di(quinolin-8-yl)pyridine); ptpy = 4'-phenyl-2,2':6',2''-terpyridine) have been investigated as photosensitizers (PSs) for photodynamic therapy (PDT). In our experimental settings, the phototoxicity and photo-index (PI) of 2 (IC50(light): 25.3 μM, 420 nm, 6.95 J/cm 2 ; PI: >4) and particularly of 1 (IC50(light): 0.62 μM, 420 nm, 6.95 J/cm 2 ; PI: 80) are considerably superior compared to the two clinically approved PSs porfimer sodium and 5-aminolevulinic. Cellular uptake and distribution of these complexes was investigated by confocal microscopy (1) and by inductively coupled plasma-mass spectrometry (1 and 2). Their phototoxicity was also determined against the Gram-(+) S. aureus and Gram-(−) E. coli for potential antimicrobial PDT (aPDT) applications. Both complexes showed significant aPDT activity (420 nm, 8 J/cm 2 ) against Gram-(+) (S. aureus; >6 log10 CFU reduction) and, for 2, also against Gram-(−) E. coli (>4 log10 CFU reduction). 3Introduction.

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“…Partial hydrolysis of 3 during 392 synthesis of ruthenium(II) complexes is known to occur under conditions of 393 high temperature reflux 20 or heating in DMF at 60 o C. 27 The second 394 hydrolysis step to the phosphonic acid needs acidic conditions or treatment 395 with Me3SiBr. The ESI mass spectrum of [Ru(Phtpy) (4) …”

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Phosphonate-functionalized heteroleptic ruthenium(II) bis(2,2′:6′,2″-terpyridine) complexes

et al. 2014

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Complexes of the Ruthenium(II)-2,2':6',2''-terpyridine Family. Effect of Electron-Accepting and -Donating Substituents on the Photophysical and Electrochemical Properties

Cited by 451 publications

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A new luminescent Ru(terpy) complex incorporating a 1,2,4-triazole based σ-donor ligand

A new luminescent Ru(terpy) complex incorporating a 1,2,4-triazole based σ-donor ligand

Synthesis, Characterization, and Biological Evaluation of New Ru(II) Polypyridyl Photosensitizers for Photodynamic Therapy

Phosphonate-functionalized heteroleptic ruthenium(II) bis(2,2′:6′,2″-terpyridine) complexes

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