Terpyridine- and 2,6-dipyrazinylpyridine-coordinated ruthenium(II) complexes: Synthesis, characterization and application in TiO2-based dye-sensitized solar cells

Vougioukalakis, Georgios C.; Στεργιόπουλος, Θωμάς; Kantonis, Georgios; Kontos, Athanassios G.; Papadopoulos, Kyriakos; Stublla, Arta; Potvin, Pierre; Falaras, Polycarpos

doi:10.1016/j.jphotochem.2010.06.001

Cited by 49 publications

(24 citation statements)

References 79 publications

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“…[3] In a similar fashion to that for H1, we prepared H2 in one step from 2-acetylpyridine and ethyl glyoxylate and isolated it as the hydrochloride salt in 60 % yield. Conversion of the ester Et2 [28] to [Ru(Et2) 2 ](PF 6 ) 2 as before was uncomplicated (82 % yield) but not so with H2. The direct reaction to produce [Ru(H2) 2 ](PF 6 ) 2 worked well and provided highpurity material, the 1 H NMR spectra of which matched those reported, [3,14] but drying the product to prepare an analytical sample resulted in a partial loss of HPF 6 , whereby the material turned a darker shade of red and became insoluble in common solvents.…”

Section: Synthesismentioning

confidence: 67%

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Ruthenium(II) Complexes of Carboxylated Terpyridines and Dipyrazinylpyridines

Stublla

Potvin

2010

Eur J Inorg Chem

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One-pot preparations of carboxylated 2,2Ј;6Ј,2ЈЈ-terpyridine and 2,6-dipyrazin-2-ylpyridine ligands are reported in free acid and ester forms, as well as their transformations to homoleptic Ru II complexes in very good yields. Density functional theory calculations of their geometry-optimized structures enabled their comparison with crystal structures; although the gross features of the crystal structures were reproduced, they showed much variability and distortion. The spectroscopic and electrochemical properties were analyzed from the point of view of their geometry-optimized struc-

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Section: Synthesismentioning

confidence: 67%

“…[27] Experimental Section General: The preparation of ligands Et2 and Et4 is reported elsewhere. [28] All reagents and solvents were reagent grade and used without further purification, except dry CH 3 CN, which was obtained by distillation with P 2 O 5 prior to use. 13 C HMBC and DEPT-135) and appear in the Supporting Information.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium(II) Complexes of Carboxylated Terpyridines and Dipyrazinylpyridines

Stublla

Potvin

2010

Eur J Inorg Chem

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“…It is therefore difficult to find a correlation between the theoretical data and the experimental ones within all the BD_nHx complexes; in Table 2 we have collected all the experimental data found in literature, indicating the reference electrode used for the experiment. [1,18,24,26,54,55] The experimental GSOP values show a decrease of 0.22 eV going from the fully protonated species to the completely deprotonated one. A good agreement is found between theoretical and experimental data, computing a decrease in GSOP from BD_3H to BD_0H of 0.30 eV, even though within the series discrepancies are retrieved in the absolute value rather than in the qualitative trend.…”

Section: Ground and Excited State Oxidation Potentialsmentioning

confidence: 92%

“…In this respect, [Ru(H 3 tcterpy)(NCS) 3 ] -(tcterpy=4,4',4"-tricarboxy-2,2':6',2"terpyridine), [1,9] also known as N749 or Black Dye (BD), has attracted considerable experimental interest. [17][18][19][20][21][22][23][24][25][26] As a matter of fact, BD is nowadays employed in the DSC that provides the highest certified efficiency of 11.4%. [15] One interesting feature of the BD is the demonstrated sensitivity of these system properties to the solution pH.…”

Section: Introductionmentioning

confidence: 99%

Everything you always wanted to Know about Black Dye (but Were Afraid to Ask): A DFT/TDDFT Investigation

Fantacci¹,

Lobello

Angelis³

2013

Chimia

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We report an exhaustive theoretical and computational investigation of the electronic, optical, redox and acid-base properties, along with the adsorption mode on TiO2, of Black Dye (BD), the prototypical panchromatic dye for solar cell applications. We investigated in detail the variation of the relevant dye properties as a function of the solution pH, corresponding to the stepwise deprotonation of the carboxylic groups. Our results reproduced the expected blue-shift of the optical absorption spectrum and the experimental trend of oxidation potentials by increasing pH, which turned both out to be in excellent agreement with experimental values. Also, our calculated excited state oxidation potential is in good agreement with available experimental data. We then looked at the pKa of the various deprotonation steps, finding lowest pKa values for the stepwise dissociation of three protons of 2.71, 3.69 and 5.20, in excellent agreement with experimental pKa values of 3 and 5, for two and one protons dissociation, respectively. We finally investigated the adsorption of BD on TiO2, finding the most stable adsorption to occur via two dissociated monodentate carboxylic groups. Inspection of the electronic structure and alignment of energy levels for N719 and BD revealed a reduced driving force for electron injection in the latter dye, which could possibly lead to energetically unfavorable electron transfer from the excited dye to the TiO2 conduction band. Our results may constitute a reference study for future investigations and optimization of BD-based dye-sensitized solar cells.

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“…As a part of our ongoing research activity on the synthesis and photoinitiated applications of transition‐metal compounds , we have recently reported a study on a novel, robust family of ruthenium‐based photosensitizers . This family of photosensitizers, bearing a new bipyridine‐type ligand of extended conjugation and an attached anthracene moiety, exhibit, upon light activation, enhanced singlet oxygen generation ability even at excitation wavelengths above 600 nm.…”

Section: Introductionmentioning

confidence: 99%

A Family of Potent Ru(II) Photosensitizers with Enhanced DNA Intercalation: Bimodal Photokillers

Pefkianakis

Theodossiou

Toubanaki

et al. 2015

Photochem & Photobiology

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A new family of Ru(II)-based photosensitizers was synthesized and systematically characterized. The ligands employed to coordinate the ruthenium metal center were the commercially available 2,2'-bipyridine and a pyridine-quinoline hybrid bearing an anthracene moiety. The complexes obtained carry either PF6- or Cl(-) counterions. These counterions determine the complexes' hydrophobic or hydrophilic character, respectively, therefore dictating their solubility in biologically related media. All photosensitizers exhibit characteristic, relatively strong and wide UV-Vis absorption spectral profiles. Their high efficiency in generating cytotoxic singlet oxygen was established (up to ΦΔ ~0.8). Moreover, the interaction of these photosensitizers with double-stranded DNA was studied fluoro- and photospectroscopically and their binding affinities were found to be of the order of 3 × 10(7) M(-1) . All complexes are photocytotoxic to DU145 human prostate cancer cells. The highest light-induced toxicity was conferred by the photosensitizers bearing Cl(-) counterions, probably due to the looser ionic "chaperoning" of Cl(-) , in comparison to PF6-, leading to higher cell internalization.

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Terpyridine- and 2,6-dipyrazinylpyridine-coordinated ruthenium(II) complexes: Synthesis, characterization and application in TiO2-based dye-sensitized solar cells

Cited by 49 publications

References 79 publications

Ruthenium(II) Complexes of Carboxylated Terpyridines and Dipyrazinylpyridines

Ruthenium(II) Complexes of Carboxylated Terpyridines and Dipyrazinylpyridines

Everything you always wanted to Know about Black Dye (but Were Afraid to Ask): A DFT/TDDFT Investigation

A Family of Potent Ru(II) Photosensitizers with Enhanced DNA Intercalation: Bimodal Photokillers

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