Betaine Dye Research Articles

Near‐Infrared Fluorescence of Novel Pyridinium−Cyclic Enolate Betaine Dyes π‐Expanded by Condensed Cyclic Thiophene Spacers

AbstractHerein, we report the synthesis of new near‐infrared (NIR) fluorescent dyes based on the pyridinium−cyclic enolate betaine (PCB) skeleton. The formation of the electron‐donor−π−electron‐acceptor (D−π−A) type dye with the electron‐donating N,N‐diphenyl amino group and the electron‐accepting PCB skeleton through a series of π−spacers allowed us to achieve NIR fluorescence. Particularly, a dye with a thienylisothianaphthene spacer showed NIR fluorescence with a significant intensity (λPL=822 nm, ΦPL=0.19 in DMSO). Detailed experimental and theoretical analyses suggested that the structural relaxation to a planar quinoidal form in the S1 state would be critical for intense NIR fluorescence.

A Collection of Dispersion Induction DI, Electrostatic ES, and Hydrogen Bonding α1 and β1 Parameters for 380 Solvents and What They Say on Solvent Effects on Rates, Equilibria, and Spectra.

The solvent parameters DI, ES, α1, and β1 are intended for the description of solute-solvent intermolecular forces, i.e., dispersion-induction, electrostatic, hydrogen-bond donation, and hydrogen-bond acceptance, respectively. An up-to-date collection of these parameters is presented for 380 solvents including green solvents, ionic liquids, and deep eutectic solvents. Their determination for additional solvents requires three commercial indicators, betaine dye B(30), 4-F-phenol, and 4-F-anisole (as well as the refractive index). The chemical significance of these parameters is outlined. Their use in the linear solvation energy relationship P = P° + di DI + e ES + a α1 + b β1 for 62 physicochemical properties P (reaction rates, equilibrium constants, and IR, UV, and NMR spectra) yields determination coefficients generally greater than 0.90 and regression coefficients whose sign and relative magnitude provide consistent information on the intermolecular forces acting on these properties.

Role of Singles Amplitudes in ADC(2) and CC2 for Low-Lying Electronically Excited States.

The closely related second-order methods CC2 and ADC(2) usually perform very similarly for single excitations of organic molecules. However, as rationalized in this work, significant deviations between these two methods can arise if the ground state and a low-lying singly excited state arise from a strong coupling between their leading configurations. Such a configuration mixing is partially accounted for in CC2 through the ground-state singles amplitudes but is omitted in ADC(2). This can cause unusual deviations between the results obtained with these methods. In this work, we study how severe this effect can become at the example of two solvatochromic dyes: the negatively solvatochromic betaine dye N1-tBu and the positively solvatochromic bithiophene P1. These two dyes allow one to study the limits of both small and somewhat larger excitation energies and configuration mixing by tuning the S0 → S1 transition energy through the polarity of the environment. Higher-level calculations at the CC3 level provide information on the accuracy of ADC(2) and CC2 in these cases. The most extreme deviation between ADC(2) and CC2 is found for N1-tBu in vacuum, where the ADC(2) result is 0.45 eV below that of CC2. In this case, the methodical error of CC2 with respect to CC3 is only 0.05 eV. With increasing excitation energy in polar solvents, the CC2-ADC(2) deviation decreases and reaches a value of only 0.15 eV. For P1, which has larger excitation energies, these effects are reversed due to the opposite solvatochromism but also smaller in magnitude: the deviation increases from 0.08 eV in vacuum to 0.16 eV in the so-called conductor limit of the continuum solvation model. Although for these two dyes larger deviations are observed for smaller excitation energies, the extent of configuration mixing does not generally correlate with only the size of excitation energy. For example, s-triazine (0.15 eV), formamide (0.19 eV), and formaldehyde (0.23 eV) also show large deviations between CC2 and ADC(2) despite their much higher excitation energies compared to those of N1-tBu and P1.

Study of the Ternary Mixture of Methanol/Formamide/Acetonitrile via Solvatochromic Probes.

Following previous studies, the ternary mixture of methanol/formamide/acetonitrile (MeOH/Formamide/MeCN) was studied using the UV-Vis absorption spectra at 298.15 K with a set of five probes, 4-nitroaniline, 4-nitroanisole, 4-nitrophenol, N,N-dimethyl-4-nitroaniline and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio)phenolate (Reichardt betaine dye), for a total of 22 mole ternary fractions. In addition, nine mole fractions of the underling binary mixtures, MeOH/Formamide and Formamide/MeCN were also tested. Spectroscopic results were used to model the preferential solvation order for each probe in the mixtures. The Kamlet-Taft solvatochromic solvent parameters, α, β, and π*, were also computed through the use of the solvatochromic shifts of the five probe indicators. Moreover, discrepancies in the spectroscopic behavior of 4-nitrophenol in formamide-rich mixtures were observed and analyzed.

Water detection in organic solvents using a copolymer membrane immobilised with a fluorescent intramolecular charge transfer-type dye: effects of intramolecular hydrogen bonds.

Numerous fluorescent dye-based optical sensors have been developed to detect water in organic solvents. However, only a few such sensors can detect water in polar solvents such as methanol or dimethyl sulfoxide, and their detection range is generally narrow. Therefore, in this study, a copolymer membrane incorporated with a pyridinium betaine dye (denoted PB1), which exhibited intramolecular charge transfer (ICT) characteristics, was developed to realise simple water detection in organic solvents. The pyridinium betaine structure, comprising intramolecular hydrogen bonds between the oxygen in the maleimide moiety and the hydrogen in the pyridinium, was vital for achieving efficient fluorescence emission. The membrane was prepared by copolymerising PB1 with the N,N-dimethyl acrylamide/acrylamide monomer on a glass plate, and the fluorescence in water-mixed organic solvents was investigated (λabs = 490 nm, λfl = 630 nm). The fluorescence intensity of the dye-immobilised membrane decreased with increasing water content of the organic solvents. The detection ranges in tetrahydrofuran, ethanol, methanol, and dimethyl sulfoxide were approximately <40, <40, <40, and <60 vol% water, respectively. In contrast, membranes based on a quaternary pyridinium dye (without intramolecular hydrogen bonds) did not detect water in methanol and dimethyl sulfoxide, although it was more sensitive than PB1 in the narrow region of low water concentration in THF. Theoretical calculations corroborated the importance of the pyridinium betaine structure in detecting water in organic solvents, with the increase in polarity and the formation of intermolecular hydrogen bonds between PB1 and water found to induce molecular rotation and fluorescence quenching.

Calculated solvent reorganization entropies, free energies, and fluctuations of the energy gaps for intramolecular electron transfer and excitation of the solvatochromic dye B30.

Intramolecular electron transfer between two biphenyl groups linked by an androstane spacer and excitation of the pyridinium-N-phenolate betaine dye B30 to the first excited singlet state are studied by quantum/classical molecular-dynamics simulations at temperatures between 150 and 300K in solvents with a range of polarities. Temperature dependences of the solvent reorganization energies, free energies, entropies, and the inhomogeneous broadening of B30's absorption band are examined. The variances of fluctuations of the energy gap between the reactant and product states do not have the direct proportionality to temperature that often is assumed to hold. An explanation for the observations is suggested.

Effective Recognition of Lithium Salt in (Choline Chloride: Glycerol) Deep Eutectic Solvent by Reichardt’s Betaine Dye 33

Deep eutectic solvents (DESs) have emerged as novel alternatives to common solvents and VOCs. Their employment as electrolytes in batteries has been an area of intense research. In this context, understanding changes in the physicochemical properties of DESs in the presence of Li salts becomes of utmost importance. Solvatochromic probes have the potential to gauge such changes. It is reported herein that one such UV–vis molecular absorbance probe, Reichardt’s betaine dye 33, effectively manifests changes taking place in a DES Glyceline composed of H-bond accepting salt choline chloride and H-bond donor glycerol in a 1:2 molar ratio, as salt LiCl is added. The lowest energy intramolecular charge–transfer absorbance band of this dye exhibits a 17 nm hypsochromic shift as up to 3.0 molal LiCl is added to Glyceline. The estimated ETN parameter shows a linear increase with the LiCl mole fraction. Spectroscopic responses of betaine dye 33, N,N-diethyl-4-nitroaniline and 4-nitroaniline are used to assess empirical Kamlet–Taft parameters of dipolarity/polarizability (π*), H-bond-donating acidity (α) and H-bond-accepting basicity (β) as a function of LiCl concentration in Glyceline. LiCl addition to Glyceline results in an increase in α and no change in π* and β. It is proposed that the added lithium interacts with the oxygen of the –OH functionalities on the glycerol rendering of the solvent with increased H-bond-donating acidity. It is observed that pyrene, a popular fluorescence probe of solvent polarity, does respond to the addition of LiCl to Glyceline, however, the change in pyrene response starts to become noticeable only at higher LiCl concentrations (mLiCl ≥ 1.5 m). Reichardt’s betaine dye is found to be highly sensitive and versatile in gauging the physicochemical properties of DESs in the presence of LiCl.

Peculiarities of solvatochromism of 4-[[(2,4-dinitrophenyl)methylene]imino-2,6-diphenyl]phenol and Reichardt’s dye. DFT calculations

One of the current directions of development of modern physical chemistry is the working out of sensor devices and molecular probes for the study of various properties of solutions, colloidal systems and biological objects. The latter include solvatochromic dyes, which, thanks to Reichardt's classic works, have found wide application for quantitative assessment of the solvating ability of individual and, to a lesser extent, mixed solvents of various nature. The different behavior of Reichardt and 4-[[(2,4-dinitrophenyl)methylene]imino-2,6-diphenyl]phenol dyes in pure water and mixed water-organic solvents, when their composition is changed, indicates that their electronic structure undergoes a fundamental change during the transition from the ground state to the first excited state. The aim of the work was to study and compare the HOMO and LUMO structure of the standard Reichardt betaine dye and the 4-[[(2,4-dinitrophenyl)methylene]imino-2,6-diphenyl]phenol dye using the stationary and time-dependent density functional theory (DFT). It is proved that the 4-[[(2,4-dinitrophenyl)methylene]imino-2,6-diphenyl]phenol dye has two active exchangeable solvation centers and therefore has an excellent solvation mechanism, at least in aqueous solution, compared to Reichardt dye, which should appear upon its solvation also in mixed water-organic solvents with a high water content in them.

Theoretical, Semiempirical, and Experimental Solvatochromic Comparison Methods for the Construction of the α1 Scale of Hydrogen-Bond Donation of Solvents.

Today, the hydrogen bonding donation (HBD) ability parameter of new solvents, α, is generally determined either by the Kamlet-Taft solvatochromic comparison of two probes, Reichardt betaine dye B(30) and 4-nitroanisole, or by the measurement of a single probe (e.g., solvatochromism of an iron coordination complex). This work highlights the shortcomings of these probes and recommends three replacement methods: (a) the theoretical comparison of the experimental and PCM-TD-DFT calculated transition energies ET(30) of B(30), (b) the semiempirical comparison of the experimental and McRae calculated ET(30), and, (c) for ionic liquids, the experimental comparison of ET(30) and ET(33) lying on the lower basicity of the betaine dye B(33) compared to B(30). These methods yield a new HBD parameter, α1, for 101 molecular solvents and 30 ionic liquids. The novelty is emblematic for water, with α1 = 1.54 instead of α (Kamlet-Taft) = 1.17. The solvent parameter α1 is not equivalent to the solute hydrogen-bond acidity parameter α2H, partly because of the self-association of HBD solvents.

Micro- vs Macrosolvation in Reichardt's Dyes.

Solvation is a complex phenomenon involving electrostatic and van der Waals forces as well as chemically more specific effects such as hydrogen bonding. To disentangle global solvent effects (macrosolvation) from local solvent effects (microsolvation), we studied the UV-vis and IR spectra of a solvatochromic pyridinium-N-phenolate dye (a derivative of Reichardt's dye) in rare gas matrices, in mixtures of argon and water, and in water ice. The π-π* transition of the betaine dye in the visible region and its C-O stretching vibration in the IR region are highly sensitive to solvent effects. By annealing argon matrices of the betaine dye doped with low concentrations of water, we were able to synthesize 1:1 water-dye complexes. Formation of hydrogen-bonded complexes leads to small shifts of the π-π* transition only, as long as the global polarity of the matrix environment does not change. In contrast, changes of the global polarity result in large spectral band shifts. Hydrogen-bonded complexes of the betaine dye are more sensitive to global polarity changes than the dye itself, explaining why ET values determined with Reichardt's dyes are very different for protic and nonprotic solvents, even if the relative permittivities of these solvents are similar.

Photophysical properties of 4-(5-methylthiophen-2-yl)pyridinium–cyclic enolate betaine dyes tuned by control of twisted intramolecular transfer

In this paper, thienylpyridinium–cyclic enolate betaine (TPB) dyes were reported as unique skeletons of fluorescent donor–acceptor type molecules.

Deep eutectic solvents in separations: Methods of preparation, polarity, and applications in extractions and capillary electrochromatography

Deep eutectic solvents (DESs) have emerged as alternatives to conventional organic solvents and ionic liquids (ILs). Their tunable and designer physio-chemical properties, low cost, and ease of preparation make them attractive solvent systems for use in extractions and additives to chromatographic separations. However, due to the diverse range of hydrogen bond acceptors and donors that comprise DESs, choosing the appropriate solvent for separations can be challenging. This review discusses all methods of DES preparation and details their advantages and disadvantages. Since polarity is an important aspect in their use in separations, the classification of DESs based on the betaine dye and nile red scales as well as Kamlet-Taft parameters is also discussed. Finally, a summary of applications of DESs in various extraction processes (phenolics, fuels, metals, proteins, carbohydrates), solid-phase extraction, solid-phase microextraction, as well as capillary electrochromatography is provided.

A Study of the Reichardt $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ Parameter using Solvent Molecular Properties Derived from Computation Chemistry and Consideration of the Kamlet and Taft α Scale of Solvent Hydrogen Bond Donor Acidities

Reichardt’s normalized $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ parameter for solvent polarity has been analyzed in terms of properties of solvent molecules estimated from quantum–mechanical calculations of isolated solvent molecules. The analyses show that $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ has a strong dependence on the partial charge on the most positive hydrogen atom in the solvent molecule, reflecting hydrogen bonding at the pendant oxygen atom of the betaine dye used to define the ET(30) scale. There are smaller, and roughly equal, dependences on the dipole moments and quadrupolar amplitudes of the solvent molecules and an inverse dependence on the solvent polarizability. These three dependences reflect the solvent polarity, that is, the ability to stabilize charge through longer-range interactions. The reason for the inverse dependence on the solvent polarizability is unclear, but a similar dependence was found previously in the analysis of the Kamlet, Abboud and Taft π* scale. The resulting equation for $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ reproduces the experimental values for around 160 solvents, representing most classes of organic solvents, with a standard deviation of around 0.07 { $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ values range from 0 to 1}. The Kamlet and Taft α scale of hydrogen bond donor acidities, which is, in effect, derived from the differences between the $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ and π* values for a solvent, is discussed. The results of the present analyses of $$E_{{\text{T}}}^{{\text{N}}} \left( {30} \right)$$ and earlier analyses of π* indicate that, while the α values capture the effect of solvent hydrogen bond donor acidity, it also contains residual dependences on other molecular properties. These residual dependences result from the differences in the dependences of the $$E_{{\text{T}}}^{{\text{N}}} \left({30} \right)$$ and π* on solvent properties.

Functionalization at C2, C3, and C4 of quinolines: Discovery of water-soluble betaine dyes of C3 quinolinium derivatives with solvatochromic and pH-sensitive properties

During functionalization at C2, C3, and C4 of quinoline, we came across a one-step metal free synthesis of C3 quinolinium derivatives of mesomeric betaine dyes. Some mesomeric betaine dyes had solvatochromic properties, and were sensitive to pH and solvates in the water. Certain betaine dyes had different properties in acidic and basic environments; the reversible interconversion between yellow (neutral or basic condition) and colorless (acidic condition) forms of the dye occurs by pH change. The changes in UV absorbance intensities of the dyes in the presence of cyclodextrins indicated the inclusion complex formation between cyclodextrins and dyes. The betaine dyes were partially dissolved in water due to the presence of positive and negative charges in the molecule. These betaine dyes did not exhibit cytotoxic activity, hence may be used in biological research.

Natural ink production and printability studies for smart food packaging

AbstractVersatile smart packages provide information on the freshness of the content and help protect the content from microorganisms. In this sense, in this study both natural antimicrobial properties and pH sensitive natural dyes were obtained from red beet. Inks were prepared and printed using this dye and their suitability for smart packaging was investigated. For this purpose, red beet was cut into small sizes and mixed separately in ethanol and water (1:2) at 200 rpm. The betaine dye was taken up in solvent. These solvents were removed with evaporator and precipitated with centrifugation and dried in a vacuum oven. The chemical structure of the obtained dye was illuminated by Attenuated Total Reflection‐Fourier Transform Infrared Spectroscopy (ATR‐FTIR). The color character was determined by UV spectroscopy. Pink colored natural ink was produced by using ink varnish with carboxymethyl cellulose polymer and solid dye. Screen printing was made with this ink and the color, gloss, and lightfastness characters of prints were examined. Antimicrobial effects of the obtained prints were measured against Staphylococcus aureus and Escherichia coli. Mordanting studies were performed with (KAl[SO4]2.12H2O) and change in color character was measured. The prints produced using the red beet extract have a yellow‐orange color in the basic state; in acid cases it was determined to have a pink‐purple color. In addition, it has been found that the ink prints obtained from red beet have antimicrobial properties against bacteria. Results prove that produced samples have good antimicrobial, pH indicator, and printability properties. This colorant can be used in smart food packaging.

Complementary interpretation of ET(30) polarity parameters of ionic liquids.

Reichardt's empirical ET(30) polarity parameter has been established as appropriate polarity scale for ionic liquids. In this study, the relationships of ET(30) of ionic liquids with the empirical Kamlet-Taft polarity parameters α (hydrogen bond donating ability), β (hydrogen bond accepting ability) and π* (dipolarity/polarizability) as well as Catalán's parameter set SA (solvent acidity), SB (solvent basicity), SP (solvent polarizability) and SdP (solvent dipolarity) are examined by means of multiple square correlation analyses. Several subtasks were carried out to address this main concern. First, the influence of anion structure on ET(30) polarity parameters for various ionic liquids are investigated by use of nine differently substituted pyridinio phenolate betaine dyes of the Reichardt type. It is assumed that halide anions can have an effect on the ET(30) parameter. In the second part, the Kamlet-Taft π* parameters have been independently determined for several protic ionic liquids using 4-tert-butyl-2-(dicyanomethylene)-5-[4-(diethylamino)-benzylidene]-Δ3-thiazoline (Th) and N,N-diethyl-4-nitroaniline (DENA) to show the impact of the hydrogen bond donating ability of the IL on the actual π* values as function of probe. α and SA values have been measured using the dicyano-bis(1,10-phenanthroline) iron(ii) complex (Fe) as HBD probe. Finally, the newly determined Reichardt ET(30), Kamlet-Taft and Catalán parameters of ionic liquids were used in addition to literature data to prove correlations of ET(30) with α and π* as well as of ET(30) with SA and SdP. Linear correlations of SdP with the molar concentration of the ionic liquid are highlighted.

Solvatochromism in some cosolvent mixtures of sulfolane and aliphatic alcohols: a tool to predict preferential solvation

The phenomenon of solvatochromism for three indicator solutes, namely para-nitroaniline, N,N-dimethyl-p-nitroaniline, and the betaine dye 4-(2,4,6-triphenylpyridinium-1-yl)-2,6-diphenylphenolate, was studied at 303.15 ± 0.1 K by means of UV–vis absorption measurements. The spectral shifts of these dyes in different mole fractions (0.0–1.0) of binary mixtures of sulfolane with eight alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol) were analyzed to investigate preferential solvation of them in terms of both the solute–solvent and the solvent–solvent interactions. A modified theoretical model (solvent exchange model) was successfully employed to calculate preferential solvation parameters and to obtain information into the contribution of intermolecular interactions to the local and bulk mole fraction distribution of solvation species. It was found that the solvation shell of the dyes is mainly affected by the solvent–solvent interactions, and in all binary mixtures, the studied solvation behavior was non-ideal.

Polarization Effects in Organic Dipole Photomotors

Brownian dipole photomotors derived from betaine and merocyanine dyes are examined. With a specific type of molecular photoexcitation and a specific relationship of the dipole moments of the ground and excited states, directed motion of the photomotor becomes symmetry-forbidden; the forbiddenness can be removed by molecular polarization effects. These effects become the predominant factor governing the direction of the motion and average velocity of photomotors, which can be an order of magnitude greater than for already known Brownian motors. These findings suggest guidelines for the molecular design of dipole photomotors with desired properties.

Spectral Study of Intermolecular Interactions in Some Sulfolane/Alcoholic Binary Mixtures Using Solvatochromic Measurements

Solvatochromic parameters including the Kamlet–Abboud–Taft parameters (α, β, and π*: KAT parameters) and Reichardt’s polarity scale (ET(30)) were measured spectroscopically over the whole mole fraction range of binary mixtures of sulfolane and some alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol) at 303.15 K. These parameters were obtained based on UV–Vis absorbance of some solvatochromic probes. The spectral changes of these indicators were interpreted in terms of specific and nonspecific dye–solvent interactions. The parameter ET(30) was obtained from electronic absorbance of the betaine dye within the mixtures. Absorbance band shifts of N,N-dimethyl-4-nitroaniline and 4-nitroaniline in concert with absorbance changes of Reichardt’s betaine dye were used to obtain dipolarity/polarizability (π*), hydrogen-bond donating (HBD) acidity (α) and hydrogen-bond accepting (HBA) basicity (β) of the mixtures. The Redlich–Kister equation was applied to the experimental data for different empirical solvatochromic parameters to demonstrate the effect of solvent composition on these parameters in the mixtures.

Synthesis of novel betaine dyes for multi chromic sensors

In this study, we have designed and synthesized novel betaine dyes with clear structural confirmation using 1H and 13C NMR spectroscopy, ESI-MS and UV–Vis analyses. For these betaines, we investigated their hydro-, iono-, thermo- and solvato-chromic sensor properties through UV–visible spectral changes and visual color changes. We observed hydrochromic properties in solution state by adding 3% water (V/V) and we checked solid state hydrochromic sensing property through betaine-embedded PEO film. For ionochromism, we used an equimolar concentration of salt to dye in solution. Thermochromic sensing studies were performed in a temperature range from 50 °C to −10 °C, and solvatochromism properties were investigated by increasing polarity using solvents from DCM to DMF. Finally, the experimental results were supported with theoretical studies.