Solvatochromism and Preferential Solvation of 4-Pentacyanoferrate 4′-Aryl Substituted Bipyridinium Complexes in Binary Mixtures of Hydroxylic and Non-hydroxylic Solvents

Papadakis, Raffaello; Tsolomitis, Athanase

doi:10.1007/s10953-011-9697-z

Cited by 24 publications

(13 citation statements)

References 29 publications

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“…Pinheiro et al [52] studied an intensely solvatochromic pentacyano ruthenium(II) complex with a 2,2′-bipyridine ligand and exploited its particularly high sensitivity to traces of water for its detection in aprotic solvents using merely UV-Vis spectrophotometry [47]. Dyes of this family have been used as solvatochromic probes [53,54]. Some studies by Coe et al brought 4,4′-bipyridine ligands to the fore [55].…”

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

“…Due to their intense solvatochromic behavior clearly associated with the presence of the monoquat ligands, complexes 31a-31f can probe small solvent polarity changes like those induced when altering the solvent/cosolvent ratio in binary solvent mixture (BSM). Papadakis et al showed that preferential solvation phenomena as well as specific local solvation effects can be conveniently investigated with the use of compounds 31a-31f [54,57]. Indeed, even BSMs involving very similar solvents in terms of polarity, e.g., water and formamide, or water and ethylene glycol were studied [54,57].…”

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

“…Papadakis et al showed that preferential solvation phenomena as well as specific local solvation effects can be conveniently investigated with the use of compounds 31a-31f [54,57]. Indeed, even BSMs involving very similar solvents in terms of polarity, e.g., water and formamide, or water and ethylene glycol were studied [54,57]. A characteristic response to solvent polarity and preferential solvation effects occurring in water/MeOH mixtures are shown in Figure 14c.…”

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

“…A characteristic response to solvent polarity and preferential solvation effects occurring in water/MeOH mixtures are shown in Figure 14c. Due to their large solvatochromic shifts and their high solubilities in polar organic solvents and water, complexes 31a-f could be outstanding solvent polarity indicators and probes of solute-microenvironment effects, especially useful in cases of media of high polarity [53][54][55]57].…”

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

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Mono- and Di-Quaternized 4,4′-Bipyridine Derivatives as Key Building Blocks for Medium- and Environment-Responsive Compounds and Materials

Papadakis

2019

Molecules

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Mono-and di-quaternized 4,4 -bipyridine derivatives constitute a family of heterocyclic compounds, which in recent years have been employed in numerous applications. These applications correspond to various disciplines of research and technology. In their majority, two key features of these 4,4 -bipyridine-based derivatives are exploited: their redox activity and their electrochromic aptitude. Contemporary materials and compounds encompassing these skeletons as building blocks are often characterized as multifunctional, as their presence often gives rise to interesting phenomena, e.g., various types of chromism. This research trend is acknowledged, and, in this review article, recent examples of multifunctional chromic materials/compounds of this class are presented. Emphasis is placed on solvent-/medium-and environment-responsive 4,4 -bipyridine derivatives. Two important classes of 4,4 -bipyridine-based products with solvatochromic and/or environment-responsive character are reviewed: viologens (i.e., N,N -disubstituted derivatives) and monoquats (i.e., monosubstituted 4,4 -bipyridine derivatives). The multifunctional nature of these derivatives is analyzed and structure-property relations are discussed in connection to the role of these derivatives in various novel applications.Molecules 2020, 25, 1 2 of 30 recent) underlining the high versatility of this class of compounds [9,10,[12][13][14][15]. Perhaps, the most reviewed subject regarding the viologens is their electrochromism [13,14,16]. Viologens are known to undergo one-electron reductions electrochemically ( Figure 2) yielding colorful radicals i.e., cations that are stable in the absence of O 2 . Yet, their chromism can also be triggered through various stimuli (including light, heat, solvents, presence of various chemical species, pressure, etc.). All these possibilities shape the very versatile "chromic character" of viologens and generally of 4,4 -bipyridine derivatives. Even though this "chromic character" has only recently started gaining more attention and there is an increasing number of research articles emphasizing on the alternative uses of 4,4 -bipyridine derivatives, there are no reviews in this growing area up until now. Such an attempt is presented in this review paper with an emphasis on medium-and environment-responsive compounds and materials based on 4,4 -bipyridine. Primary focus is placed on viologen-involving solvatochromic systems as well as materials and compounds of this class whose chromic behavior is dependent on various environment stimuli. Molecules 2018, 23, x 2 of 30 Figure 2. Schemes depicting (a) the electrochromic cycle (1) and (b) the photochromic cycle of paraquat (A, counter anion). Structure and Properties of Viologens The Strong Electron-Withdrawing Character of ViologensThe strong electron-withdrawing character of viologens has been widely exploited in numerous molecular architectures and materials. Viologens can undergo reversible one-electron reductions forming radical cations (Figure 2a), which are vividly colo...

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Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

Section: Solvatochromic Complexes Involving Monoquats As Ligandsmentioning

confidence: 99%

See 2 more Smart Citations

Mono- and Di-Quaternized 4,4′-Bipyridine Derivatives as Key Building Blocks for Medium- and Environment-Responsive Compounds and Materials

Papadakis

2019

Molecules

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“…The latter model does not have special requirements or limitations. − A general requirement in any case is the use of intensely medium responsive compounds as probes of the cybotactic region. Ferrocyanide(II) complex dyes involving electron withdrawing ligands such as 4,4′-bipyridine constitute a class of highly polar and intensely solvatochromic dyes, often utilized as chemical probes of dielectric and specific solute–solvent effects in neat solvents and BSMs. − The strong HBA character of the −CN groups − of ferrocyanide(II) along with the strong electron withdrawing cationic pyridinium segment utilized in various recent studies (both in free pyridinium-based cations as wells as in monoquat-ligated metal complexes) − give rise to various interactions with the solvent molecules in solution. In this work, a previously synthesized solvatochromic ferrocyanide(II) complex involving a monoquat-based ligand (compound 1 , Figure ) was utilized as a potent chromic probe for the rationalization of the solute–solvent and solvent–solvent interactions in the vicinity of solvation region in aqueous BSMs (also known as cybotactic region).…”

Section: Introductionmentioning

confidence: 99%

Preferential Solvation of a Highly Medium Responsive Pentacyanoferrate(II) Complex in Binary Solvent Mixtures: Understanding the Role of Dielectric Enrichment and the Specificity of Solute–Solvent Interactions

Papadakis

2016

J. Phys. Chem. B

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In this work, the preferential solvation of an intensely solvatochromic ferrocyanide(II) dye involving a 4,4'-bipyridine-based ligand was examined in various binary solvent mixtures. Its solvatochromic behavior was rationalized in terms of specific and nonspecific solute-solvent interactions. An exceptional case of solvatochromic inversion was observed when going from alcohol/water to amide/water mixtures. These effects were quantified using Onsager's solvent polarity function. Furthermore, the sensitivity of the solvatochromism of the dye was determined using various solvatochromic parameters such as π* expressing the dipolarity/polarizability of solvents and α expressing the hydrogen-bond-donor acidity of solvents. This analysis was useful for the rationalization of the selective solvation phenomena occurring in the three types of alcohol/water and amide/water mixtures studied. Furthermore, two preferential solvation models were employed for the interpretation of the experimental spectral results in binary solvent mixtures, namely, the model of Suppan on dielectric enrichment [J. Chem. Soc. Faraday Trans. 1 1987, 83, 495-509] and the model of Bosch, Rosés, and co-workers [J. Chem. Soc., Perkin Trans. 2, 1995, 8, 1607-1615]. The first model successfully predicted the charge transfer energies of the dye in formamide/water and N-methylformamide/water mixtures, but in the case of MeOH/water mixtures, the prediction was less accurate because of the significant contribution of specific solute-solvent interactions in that case. The second model gave more insights for both specific solute-solvent as well as solvent-solvent interactions in the cybotactic region. The role of dielectric enrichment and specific interactions was discussed based on the findings.

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2017

Cyclodextrins

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Solvatochromism and Preferential Solvation of 4-Pentacyanoferrate 4′-Aryl Substituted Bipyridinium Complexes in Binary Mixtures of Hydroxylic and Non-hydroxylic Solvents

Cited by 24 publications

References 29 publications

Mono- and Di-Quaternized 4,4′-Bipyridine Derivatives as Key Building Blocks for Medium- and Environment-Responsive Compounds and Materials

Mono- and Di-Quaternized 4,4′-Bipyridine Derivatives as Key Building Blocks for Medium- and Environment-Responsive Compounds and Materials

Preferential Solvation of a Highly Medium Responsive Pentacyanoferrate(II) Complex in Binary Solvent Mixtures: Understanding the Role of Dielectric Enrichment and the Specificity of Solute–Solvent Interactions

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