Spectral Investigations of Preferential Solvation and Solute–Solvent Interactions of Free Base and Protonated 5,10,15,20-Tetrakis(4-trimethyl-ammonio-phenyl)-porphine Tetratosylate in Aqueous Organic Mixed Solvents

Gharib, Farrokh; Shamel, Ali; Jaberi, Fatemeh; Farajtabar, Ali

doi:10.1007/s10953-013-0007-9

Cited by 15 publications

(10 citation statements)

References 31 publications

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“…S11 †). The line-shape is reproduced well by including coupling from both 59 Co nuclei, A = (3.1, 4.6, 1.5) × 10 −4 cm −1 , whose average matches the isotropic value. These EPR and electrochemical measurements suggest that oxidation of complex 2 is ligand-based, leading to the formation of a dicobalt decomposition species with a bridging benzosemiquinone radical which is sufficiently long-lived to be detected by EPR.…”

Section: Redox Chemistry Of Compoundmentioning

confidence: 53%

“…the composition of the solvent system in the cybotactic region of the solute is essentially the same as in the bulk). 58,59 In the case of dichloromethane-methanol mixtures, the absorbance of complex 2 again shifts in a linear fashion over most of the compositional range, but there is now some deviation away from ideal behaviour at high ratios of dichloromethane to methanol (above 3 : 1). This suggests that some preferential solvation of complex 2 by methanol does indeed occur.…”

Section: Solvatochromic Behaviour Of Complex 3 and Comparison To Thatmentioning

confidence: 99%

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The electronic and solvatochromic properties of [Co(L)(bipyridine)₂]⁺(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

et al. 2016

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Complexes of Co(iii) containing mixed chelating diimine and o-quinone ligand sets are of fundamental interest on account of their fascinating magnetic and electronic properties. Whilst complexes of this type containing one diimine and two o-quinone ligands have been studied extensively, those with the reverse stoichiometry (two diimines and one o-quinone) are much rarer. Herein, we describe a ready route to the synthesis of the complex [Co(o-catecholate) (2,2'-bipyridine)] (1), and also report the synthesis of [Co(o-catecholate)(5,5'-dimethyl-2,2'-bipyridine)] (2) and [Co(o-benezenedithiolate)(5,5'-dimethyl-2,2'-bipyridine)] (3) for the first time. Spectroscopic studies show that complex 2 displays intriguing solvatochromic behaviour as a function of solvent hydrogen bond donation ability, a property of this type of complex which has hitherto not been reported. Time-dependent density function theory (TD-DFT) shows that this effect arises as a result of hydrogen bonding between the solvent and the oxygen atoms of the catecholate ligand. In contrast, the sulfur atoms in the benzenedithiolate analogue 3 are much weaker acceptors of hydrogen bonds from the solvent, meaning that complex 3 is only very weakly solvatochromic. Finally, we show that complex 2 has some potential as a molecular probe that can report on the composition of mixed solvent systems as a function of its absorbance spectrum.

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Section: Redox Chemistry Of Compoundmentioning

confidence: 53%

Section: Solvatochromic Behaviour Of Complex 3 and Comparison To Thatmentioning

confidence: 99%

The electronic and solvatochromic properties of [Co(L)(bipyridine)₂]⁺(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

et al. 2016

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“…In continuous of our previous studies on porphyrin [12][13][14][15][16][17], in this work the protonation constants of 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin were determined by spectroscopic titration in binary mixtures of water with N,N-dimethylformamide, DMF, to examine the solvent dependence of its acid-base properties. Spectroscopic titration is a convenient way for accurate determination of equilibrium constants [18][19][20].…”

Section: Introductionmentioning

confidence: 99%

Solvent effect on protonation of tpps in water-DMF mixtures

Farajtabar¹,

Faeli²

2017

Bull. Chem. Soc. Eth.

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ABSTRACT. The protonation of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin was investigated in aqueous solutions of N,N-dimethyformamide at 25 C and 0.1 mol.dm -3 sodium perchlorate. The solvent effect on value of protonation constant was examined by using the linear solvation energy relationship concept. The value of logK1, logK2 and logKt was correlated with the macroscopic (dielectric constant) and microscopic Kamlet-Taft parameters (,  and *) of binary mixtures. The solvent effects were analyzed in the terms of Kamlet, Abboud and Taft model (KAT). Multiple linear regression were used to find the contribution of the microscopic parameters containing  (hydrogen-bond acidity), * (dipolarity/polarizability) and  (hydrogen-bond basicity). It was found that  and  were the most predominant descriptors. Also, relationship with reciprocal of dielectric constant was obtained based on Born's model, showing the significance of specific solute-solvent interactions. Therefore the hydrogen bonding interactions between solute and solvent components are mainly responsible for the change in protonation constants of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin in water-N,N-dimethyformamid binary mixtures.

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“…In addition, solvent-solvent interactions may affect the type and extent of the solute-solvent interactions. [1][2][3][4][5][6][7][8]…”

Section: Introductionmentioning

confidence: 99%

Solvatochromism of naringenin in aqueous alcoholic mixtures

Faraji

Farajtabar

2016

JSCS

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The spectral change of naringenin in binary mixtures of water with methanol, ethanol or 1-propanol was studied by UV-Vis spectrophotometry at 25 °C. The effect of the solvent was investigated by analysis of the electron transition energy at the maximum absorption wavelength as a function of the Kamlet and Taft parameters of the mixtures by means of linear solvation energy relationships. The nonlinear response of the solvatochromism was explained based on solute-solvent and solvent-solvent interactions. The possible preferential solvation of naringenin by each of the solvents was studied through a modified preferential solvation model that considers the hydrogen bonding interactions between the prior solvents due to solvent-solvent interactions. The preferential solvation parameters and local mole fraction distribution around the solute were calculated. The results indicated that naringenin prefers to be more solvated by the complex solvating species and organic solvents than water.

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Spectral Investigations of Preferential Solvation and Solute–Solvent Interactions of Free Base and Protonated 5,10,15,20-Tetrakis(4-trimethyl-ammonio-phenyl)-porphine Tetratosylate in Aqueous Organic Mixed Solvents

Cited by 15 publications

References 31 publications

The electronic and solvatochromic properties of [Co(L)(bipyridine)₂]⁺(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

The electronic and solvatochromic properties of [Co(L)(bipyridine)₂]⁺(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

Solvent effect on protonation of tpps in water-DMF mixtures

Solvatochromism of naringenin in aqueous alcoholic mixtures

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Spectral Investigations of Preferential Solvation and Solute–Solvent Interactions of Free Base and Protonated 5,10,15,20-Tetrakis(4-trimethyl-ammonio-phenyl)-porphine Tetratosylate in Aqueous Organic Mixed Solvents

Cited by 15 publications

References 31 publications

The electronic and solvatochromic properties of [Co(L)(bipyridine)2]+(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

The electronic and solvatochromic properties of [Co(L)(bipyridine)2]+(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

Solvent effect on protonation of tpps in water-DMF mixtures

Solvatochromism of naringenin in aqueous alcoholic mixtures

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The electronic and solvatochromic properties of [Co(L)(bipyridine)₂]⁺(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study

The electronic and solvatochromic properties of [Co(L)(bipyridine)₂]⁺(L = o-catecholato, o-benzenedithiolato) species: a combined experimental and computational study