Whole microwave syntheses of pyridylpyrazole and of Re and Ru luminescent pyridylpyrazole complexes

Merillas, Beatriz; Cuéllar, Elena; Diez‐Varga, Alberto; Asensio-Bartolomé, Miryam; Garcı́a-Herbosa, Gabriel; Torroba, Tomás; Martín‐Alvarez, José M.; Miguel, Daniel; Villafañe, Fernando

doi:10.1016/j.ica.2018.09.002

Cited by 8 publications

(12 citation statements)

References 108 publications

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“…These assignments are based on the absorption spectra of closely related metal complexes, which display similar bands, such as 271 and 352 nm for 1 in CHCl 3 . 15 The similar high-energy MLCT transitions displayed by 1 and 3a−d or 4a−d (ca. 355 nm, see Table 1) indicates that the replacement of a bromido ligand in 1 by different pyrazoles (complexes 3a−d) does not seem to affect the dπ(Re) orbital energy.…”

Section: Inorganic Chemistrymentioning

confidence: 92%

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO₂ Reduction Electrocatalysts

et al. 2020

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Cationic fac-[Re(CO) 3 (pz*H)(pypzH)]OTf (pz*H = pyrazole, pzH; 3,5-dimethylpyrazole, dmpzH; indazole, indzH; 3-(2-pyridyl)pyrazole, pypzH) were obtained from fac-[ReBr(CO) 3 (pypzH)] by halide abstraction with AgOTf and subsequent addition of the corresponding pyrazole. Successive deprotonation with Na 2 CO 3 and NaOH gave neutral fac-[Re(CO) 3 (pz*H)(pypz)] and anionic Na{fac-[Re(CO) 3 (pz*)-(pypz)]} complexes, respectively. Cationic fac-[Re(CO) 3and fac-[Re(CO) 3 (pypz) 2 Na] were subjected to photophysical and electrochemical studies. They exhibit phosphorescent decays from a prevalently 3 MLCT excited state with quantum yields (Φ) in the range between 0.03 and 0.58 and long lifetimes (τ from 220 to 869 ns). The electrochemical behavior in Ar atmosphere of cationic and neutral complexes indicates that the oxidation processes assigned to Re I → Re II occurs at lower potentials for the neutral complex compared to cationic complex. The reduction processes occur at the ligands and do not depend on the charge of the complexes. The electrochemical behavior in CO 2 saturated media is consistent with CO 2 electrocatalyzed reduction, where the values of the catalytic activity [i cat (CO 2 )/i cat (Ar)] ranged from 2.7 to 11.5 (compared to 8.1 for fac-[Re(CO) 3 Cl(bipy)] studied as a reference). Controlled potential electrolysis for the pyrazole cationic (3a) and neutral (4a) complexes after 1 h affords CO in faraday yields of 61 and 89%, respectively. These values are higher for indazole complexes and may be related to the acidity of the coordinated pyrazole.

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Section: Inorganic Chemistrymentioning

confidence: 92%

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO₂ Reduction Electrocatalysts

et al. 2020

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“…Solvents were purified according to standard procedures. cis -[Ru(bipy) 2 Cl 2 ] was obtained as previously described by our group. All other reagents were obtained from the usual commercial suppliers and used as received.…”

Section: Methodsmentioning

confidence: 99%

“…In addition, the use of 1,2-azole ligands will favor the future tunability of the complexes in both ground and excited states. We have shown how a systematic control of the electronic and steric properties of other metal transition complexes containing 1,2-azoles and their derivatives that allows to tune properties of interest, such as their selectivity toward anions, 50 their luminescent properties, 51,52 or their activity as electrocatalysts in CO 2 reduction. 53 Herein we report the synthesis and a thorough characterization of new (1,2-azole)-aquo bis(bipyridyl)ruthenium(II) complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

(1,2-Azole)bis(bipyridyl)ruthenium(II) Complexes: Electrochemistry, Luminescent Properties, And Electro- And Photocatalysts for CO₂ Reduction

et al. 2020

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New cis-(1,2-azole)-aquo bis(2,2′-bipyridyl)ruthenium(II) (1,2-azole (az*H) = pzH (pyrazole), dmpzH (3,5-dimethylpyrazole), and indzH (indazole)) complexes are synthesized via chlorido abstraction from cis-[Ru(bipy)2Cl(az*H)]OTf. The latter are obtained from cis-[Ru(bipy)2Cl2] after the subsequent coordination of the 1,2-azole. All the compounds are characterized by 1H, 13C, 15N NMR spectroscopy as well as IR spectroscopy. Two chlorido complexes (pzH and indzH) and two aquo complexes (indzH and dmpzH) are also characterized by X-ray diffraction. Photophysical and electrochemical studies were carried out on all the complexes. The photophysical data support the phosphorescence of the complexes. The electrochemical behavior of all the complexes in an Ar atmosphere indicate that the oxidation processes assigned to Ru(II) → Ru(III) occurs at higher potentials in the aquo complexes. The reduction processes under Ar lead to several waves, indicating that the complexes undergo successive electron-transfer reductions that are centered in the bipy ligands. The first electron reduction is reversible. The electrochemical behavior in CO2 media is consistent with CO2 electrocatalyzed reduction, where the values of the catalytic activity [i cat(CO2)/i p(Ar)] ranged from 2.9 to 10.8. Controlled potential electrolysis of the chlorido and aquo complexes affords CO and formic acid, with the latter as the major product after 2 h. Photocatalytic experiments in MeCN with [Ru(bipy)3]Cl2 as the photosensitizer and TEOA as the electron donor, which were irradiated with >300 nm light for 24 h, led to CO and HCOOH as the main reduction products, achieving a combined turnover number (TONCO+HCOO– ) as high as 107 for 2c after 24 h of irradiation.

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“…Compared with conventional reflux approaches, microwave reactions require short reaction time, exhibit superior operational simplicity and are highly reproducible. [ 26,27 ] Five organotin complexes were derived with a yield of approximately 70%, which indicated considerable improvement of productivity. The ‘one‐pot’ approach required a reaction time of 30 min.…”

Section: Resultsmentioning

confidence: 99%

One‐pot microwave‐assisted synthesis of dialkytin 2‐[(4‐methylbenzoyl) hydrazono]‐3‐phenylpropanoic acid complexes and their anticarcinoma activities and DNA‐binding properties

Jiang

Tan

Peng

2022

Applied Organom Chemis

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Under microwave irradiation, five organotin complexes were produced through the reaction of 4‐methylbenzhydrazide, sodium phenylpyruvate and corresponding dialkyltin. Fourier transform infrared spectroscopy; 1H, 13C and 119Sn nuclear magnetic resonance spectroscopy; high‐resolution mass spectrometry; X‐ray crystallography and thermogravimetric analysis (TGA) were performed to characterise the synthesised complexes. The in vitro antitumour activity for the complexes involved was assessed using the MTT assay on the human carcinoma cells of HepG2, NCI‐H460 and MCF7. 2‐Oxo‐3‐pheny propionic acid p‐methyl benzoylhydrazone dibutyltin, C5, exhibited an intensive anticarcinoma activity. Cell apoptosis revealed that C5 mediated the cell apoptosis of HepG2 cells. DNA binding in C5 was investigated through UV‐visible absorption spectrometry and viscosity measurement. Molecular docking was performed for predicting C5‐DNA binding, which revealed C5 could be implanted into the DNA double helix.

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Whole microwave syntheses of pyridylpyrazole and of Re and Ru luminescent pyridylpyrazole complexes

Cited by 8 publications

References 108 publications

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO₂ Reduction Electrocatalysts

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO₂ Reduction Electrocatalysts

(1,2-Azole)bis(bipyridyl)ruthenium(II) Complexes: Electrochemistry, Luminescent Properties, And Electro- And Photocatalysts for CO₂ Reduction

One‐pot microwave‐assisted synthesis of dialkytin 2‐[(4‐methylbenzoyl) hydrazono]‐3‐phenylpropanoic acid complexes and their anticarcinoma activities and DNA‐binding properties

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Whole microwave syntheses of pyridylpyrazole and of Re and Ru luminescent pyridylpyrazole complexes

Cited by 8 publications

References 108 publications

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO2 Reduction Electrocatalysts

(1,2-Azole)bis(bipyridyl)ruthenium(II) Complexes: Electrochemistry, Luminescent Properties, And Electro- And Photocatalysts for CO2 Reduction

One‐pot microwave‐assisted synthesis of dialkytin 2‐[(4‐methylbenzoyl) hydrazono]‐3‐phenylpropanoic acid complexes and their anticarcinoma activities and DNA‐binding properties

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Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO₂ Reduction Electrocatalysts

Luminescent Rhenium(I)tricarbonyl Complexes Containing Different Pyrazoles and Their Successive Deprotonation Products: CO₂ Reduction Electrocatalysts

(1,2-Azole)bis(bipyridyl)ruthenium(II) Complexes: Electrochemistry, Luminescent Properties, And Electro- And Photocatalysts for CO₂ Reduction