Reichardt's Dye Research Articles

Solvatochromism in Mixtures of Hydrogen Bond Acceptor (HBA) Solvents with Water.

The UV/Vis absorption energies νmax of Reichardt's dye B30 with respect to ET(30) and 4-nitroaniline (NA) are investigated as a function of the solvent composition Nav,z. in co-solvent/water mixtures. Nav,z. is the average molar concentration of the solvent mixture at a given solvent fraction z. The z can be the mole, the volume or the mass fraction. The co-solvents considered were acetonitrile, acetone, tetrahydrofuran, pyridine, piperidine and 2-(diethylamino)-ethanol. Acetone and acetonitrile can be expected to slightly enhance the water structure at low co-solvent concentrations. This interpretation is supported by the analysis of the refractive index as a function of the solvent composition. In general, it can be stated that the structural complexity of the binary solvent mixtures is mainly responsible for the evolution of the absorption energies ET(30) or νmax(NA) as a function of the mixture composition. In particular, the endothermic solvation of NA in co-solvent/water mixtures and its effect on the νmax(NA) is highlighted.

Structural insight into piezo-solvatochromism of Reichardt's dye.

To date, accurate modelling of the solvation process is challenging, often over-simplifying the solvent-solute interactions. The interplay between the molecular arrangement associated with the solvation process and crystal nucleation has been investigated by analysis of the piezo-solvatochromic behaviour of Reichardt's dye, ET(1), in methanol, ethanol and acetone under high pressure. High-pressure single-crystal X-ray diffraction and UV-Vis spectroscopy reveal the impact of solute-solvent interactions on the optical properties of ET(1). The study underscores the intricate relationship between solvent properties, molecular conformation and crystal packing. The connection between liquid and solid phases emphasizes the capabilities of high-pressure methods for expanding the field of crystal engineering. The high-pressure environment allowed the determination of the crystal structures reported here that are built from organic molecules fourfold solvated with ethanol or methanol: ET(1)·4CH3OH and ET(1)·4C2H5OH·H2O. The observed piezo-solvatochromic effects highlight the potential of ET(1) in nonlinear optoelectronics and expand the application of solvatochromic chemical indicators to pressure sensors.

Extended Reichardt's Dye–Synthesis and Solvatochromic Properties

Extended Reichardt's Dye–Synthesis and Solvatochromic Properties

Entropy-Enthalpy Compensation in Electron-Transfer Processes.

Solvent reorganization energies, free energies, and entropies are obtained for photoexcitation of three molecules that exhibit strong solvatochromism [Nile red, 5-(dimethylamino)-5'-nitro-2,2-bisthiophene, and Reichardt's dye B30] by measuring their optical absorption spectra at temperatures between 150 and 300 K in solvents with a range of polarities. Energies, free energies, and entropies of solvent reorganization are also obtained from computer simulations of three intramolecular electron-transfer reactions (charge separation and recombination in Zn-porphyrin-quinone cyclophane and charge transfer in a bis-biphenylandrostane radical anion). Entropy-enthalpy compensation in the solvent reorganization free energy for photoexcitation or electron transfer is found to be essentially complete (having nearly equal and opposite contributions from entropic and enthalpic effects) for all of the processes with solvent reorganization energies less than about 0.1 eV. Compensation becomes less complete as the reorganization energy becomes larger. A semiclassical treatment of the solvent reorganization entropy can rationalize these results.

Temperature-dependent solvent reorganization entropies, free energies, and transition dipole strengths for the photoexcitation of Reichardt's dye B30.

Absorption spectra of the solvatochromic dye 2,6-diphenyl-4-2,4,6-triphenyl-1-pyridinophenolate (B30) were measured in seven solvents of varying polarity over temperature ranging from each solvent's freezing point to 300K. The excitation energies and their variances allowed calculations of the solvent reorganization energies, reorganization free energies and reorganization entropies as functions of temperature. The entropies of solvent packing around the chromophore are found to make major contributions to the reorganization free energies. The variances of the excitation energies depend only weakly on temperature, in disagreement with an expression that is often used for solvent reorganization free energies. Polar solvents reduce the transition dipole strength of B30's long-wavelength absorption band, probably because interactions with the solvent enhance the charge-transfer character of the transition. The dipole strength drops further at low temperatures.

Investigating hydrophobic environment in alkyl-group-functionalized silica particle with various chain lengths using absorption microspectroscopy.

A well-known solvatochromic dye, Reichardt's dye (R-dye), was used to evaluate the hydrophobicity of alkyl-group-functionalized silica particles (ASPs) with different chain lengths. The absorption spectra of R-dye were measured in a single ASP in a mixed solution of water and an organic solvent (methanol (MeOH), ethanol (EtOH), acetonitrile (ACN), tetrahydrofuran (THF), or N,N-dimethylformamide (DMF)) using absorption microspectroscopy. The polarity parameter in the ASPs (ET), determined by the absorption maximum, was observed to be smaller than those in bulk solutions, indicating that R-dye was present in a more hydrophobic environment. In EtOH, THF, and DMF, R-dye was distributed within the alkyl chain layer including the organic solvent. An increase in the organic solvent content of the bulk solution led to a higher organic solvent concentration in the alkyl chain layer, resulting in a decrease in ET. In MeOH and ACN, the R-dye was distributed within the alkyl chain layer and concentrated phase. Moreover, with the increase in the organic molecule content, the distribution of R-dye in the concentrated phase became dominant in MeOH and ACN system, leading to an increase in the ET value. The findings presented in this paper are expected to attract the attention of a wide range of researchers in chromatography.

Solvent Polarity under Vibrational Strong Coupling.

Vibrational strong coupling (VSC) occurs when molecular vibrations hybridize with the modes of an optical cavity, an interaction mediated by vacuum fluctuations. VSC has been shown to influence the rates and selectivity of chemical reactions. However, a clear understanding of the mechanism at play remains elusive. Here, we show that VSC affects the polarity of solvents, which is a parameter well-known to influence reactivity. The strong solvatochromic response of Reichardt's dye (RD) was used to quantify the polarity of a series of alcohol solvents at visible wavelengths. We observed that, by simultaneously coupling the OH and CH vibrational bands of the alcohols, the absorption maximum of Reichardt's dye redshifted by up to ∼15.1 nm, corresponding to an energy change of 5.1 kJ·mol-1. With aliphatic alcohols, the magnitude of the absorption change of RD was observed to be related to the length of the alkyl chain, the molecular surface area, and the polarizability, indicating that dispersion forces are impacted by strong coupling. Therefore, we propose that dispersion interactions, which themselves originate from vacuum fluctuations, are impacted under strong coupling and are therefore critical to understanding how VSC influences chemistry.

Exploring solvation behaviour of biocompatible ionic liquid 2-hydroxyethylammonium formate + polyethylene glycols mixtures: Role of oxyethylene and hydroxyl units of PEGs

The favourable modification of the physicochemical properties of the ionic liquid with green co-solvent and their molecular level characterization with spectroscopic techniques is the area of current research. Further, the co-solvent modified ionic liquid mixtures furnishes interesting properties which render the utility of these solvents in several important applications. In the current work, the effects of addition of two polyethylene glycols (PEGs) with average molecular weights of 200, and 600 on solvent properties of IL 2-hydroxyethyl ammonium formate (HEF) has been explored with the help of solvatochromic absorbance probes. The physicochemical characteristics of the ionic liquid mixtures are altered in an unexpectedly positive way when PEGs are added to IL HEF. The absorbance behaviour of the solvatochromic probes Reichardt dye 33 shows interestingly positive non-ideal behaviour, which may be attributed to the high dipolarity/polarizability (π*) and hydrogen bond donor ability (HBD) (α) of the HEF + PEG mixtures. Further, the Kamlet-Taft parameters, including hydrogen bond acceptor ability (HBA) (β), and hydrogen bond donor ability (HBD) (α), and dipolarity/polarizability (π*) of the HEF + PEG binary mixtures display nonideality, which may be because of the strong Hydrogen bond networking of HEF-PEG molecules along with solute-HEF/PEG interaction present in the mixtures. Moreover, the preferential solvation approach has been invoked to explore the solute–solvent/solvent–solvent interactions present in the HEF + PEGs binary mixtures. The Redlich–Kister (CNIBS/R–K) theoretical model predicts the experimental results obtained by solvatochromic probe studies in satisfactory manner. The results of the DFT and FTIR study also predict the possibility of the H-bonding interactions in HEF + PEGs mixtures.

Empirical Hydrogen Bonding Donor (HBD) Parameters of Organic Solvents Using Solvatochromic Probes - A Critical Evaluation.

The solvatochromicity of established solvatochromic UV/Vis probes, which appear to be sensitive to the so-called hydrogen bond donor (HBD) property of the solvent, is analysed using the hydroxyl group density of alcoholic solvents DHBD as a physical parameter in comparison to the pKa, the chemical benchmark for acidity. Reichardt's dye B30, Kosowers Z-indicator 1-ethyl-4-(methoxycarbonyl) pyridinium iodide (K), Kamlet-Tafts α, Dragos S parameter, Catalans SA scale, the cis-dicyano-bis (1,10-phenanthroline) iron II complex (Schilt's Ferrocyphen dye, Fe) and Gutmann's acceptor number (AN) have been investigated. The observed dependencies of the empirical polarity parameters as a function of DHBD for several alcoholic solvent families requires a ompletely new physicochemical understanding of these established HBD parameters. Only the AN scale (or Fe) is able to bridge the gap between global polarity and acidity, provided the values are interpreted correctly and applied accordingly.

The Negative Solvatochromism of Reichardt's Dye B30 - A Complementary Study.

The UV/Vis spectra of a hypothetical negative solvatochromic dye in a solvent are theoretically calculated assuming the classical damped harmonic oscillator model and the Lorentz‐Lorenz relation. For the simulations, the oscillator strength of the solvent was varied, while for the solute all oscillator parameters were kept constant. As a result, a simple change of the oscillator strength of the solute can explain the redshift and intensity increase of the UV/Vis band of the solute. Simulated results are compared with measured UV/Vis spectroscopic data of 2,6‐diphenyl‐4‐(2,4,6‐triphenylpyridinium‐1‐yl) phenolate B30 (Reichardt‘s dye) Significant correlations of the absorption energy (1/λmax) with the molar absorption coefficient ϵ as function of solvent polarity are demonstrated for several derivatives of B30. The approach presented is only applicable to negative solvatochromism. Therefore, while the approach is vital to fully understand solvatochromism, it needs to be complemented by other approaches, e. g., to describe the changes of the chemical interactions based on the nature of the solvent, to explain all its various aspects.

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.

Luminescence of Reichardt's dye in polyelectrolyte-modified saponite colloids

Reichardt’s dye (RD) exhibits solvatochromic properties across the entire visible spectrum. This work reports, for the first time, luminescence of RD in colloidal systems of layered silicate saponite (Sap) modified with poly(diallyldimethylammonium) polycations (PDDA), and provides an interpretation of this unique phenomenon. The application of tailored theoretical chemistry methods such as DFT and other approaches supplies a theoretical interpretation of the phenomenon to supplement the results of the experiments. RD luminescence was achieved by preventing the movement of molecules and suppressing non-radiative relaxation processes. This effect only occurred if the negatively-charged phenolate group in the RD molecule interacted with the positively-charged groups of the PDDA cations, while at the same time the positively-charged pyridinium group was also adsorbed onto the negatively-charged Sap siloxane surface. Only at small coverage of the Sap surface by PDDA cations is there sufficient fixation of the RD molecules for them to exhibit luminescent properties. The results suggest that the application of this dye may be extended to luminescent probes, which could be used to characterize the distribution of charge centers on the surfaces of various materials, biopolymers, biological tissues, etc.

Delineating solvation behaviour and molecular interactions within ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate + ethylene glycol monomethyl ether solutions

Cosolvent-modified ionic liquid (IL)-based binary mixtures have been used in several chemical applications. Therefore, the molecular-level understanding of these binary mixtures is of utmost necessity to enhance their utility in applications in several fields. This work involves the spectroscopic study of the binary mixture of the IL 1‑butyl‑3-methylimidazolium tetrafluoroborate ([bmim][BF4]) and ethylene glycol monomethyl ether (EGME) using several polarity-based absorbence and fluorescence probes (Reichardt's dye 33, pyrene, and 1-pyrene carboxaldehyde) and the microviscosity probe 9-(2,2-dicyanovinyl) julolidine (DCVJ). The behaviour of these probes hints at the synergistic behaviour of the IL–EGME mixtures. The Kamlet–Taft parameters have also been calculated and provide an understanding of the solute–solvent and/or solvent–solvent interactions. Further, the dynamic viscosity and Fourier transform infrared spectroscopy (FTIR) results suggest strong hydrogen bonding between the IL and EGME molecules. The preferential solvation model also indicates the formation of a new entity due to solvent–solvent interactions.

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.

Synthesis and Solvatochromic Behavior of Zwitterionic Donor–Bridge–Acceptor Systems with Oligo(p-phenylene) Spacers

Oligo(p-phenylene)s with a donor phenol group and an acceptor pyridinium moiety separated by one and two p-phenylene units were synthesized by the linear iterative Suzuki–Miyaura coupling method using aryl nonaflates as effective coupling reagents. Zwitterionic forms of these push–pull molecules were generated upon deprotonation of the phenol leading to large redshifts in absorbance maxima. UV-vis absorbance studies also revealed strong dependence of the band position on solvent polarity: a smooth bathochromic shift can be observed with the decrease of the solvent polarity. The molecule with one p-phenylene bridging unit showed the strongest solvatochromic characteristics in the series, spanning the range of 167 nm while moving from polar water to less polar N,N-dimethylformamide. The magnitude of this shift was close to Reichardt's dye — one of the most solvatochromic organic dyes known.

Fast Molecular Compression by a Hyperthermal Collision Gives Bond-Selective Mechanochemistry.

Using electrospray ion beam deposition, we collide the complex molecule Reichardt's dye (C_{41}H_{30}NO^{+}) at low, hyperthermal translational energy (2-50eV) with a Cu(100) surface and image the outcome at single-molecule level by scanning tunneling microscopy. We observe bond-selective reaction induced by the translational kinetic energy. The collision impulse compresses the molecule and bends specific bonds, prompting them to react selectively. This dynamics drives the system to seek thermally inaccessible reactive pathways, since the compression timescale (subpicosecond) is much shorter than the thermalization timescale (nanosecond), thereby yielding reaction products that are unobtainable thermally.

Electroconvection in Zwitterion‐Doped Nematic Liquid Crystals and Application as Smart Windows

AbstractElectroconvection (EC) in liquid crystals (LCs) is extensively studied for the formation of regular nonequilibrium structures, and the applications that require strong light scattering and high haze. Doping the LCs with ionic species has proven to be an effective method to obtain uniform and high‐quality textures. Herein, zwitterion is explored as a new class of ionic dopant that has little problem of ion accumulation as compared to typical organic electrolytes. A rich variety of EC patterns are observed and characterized for both positive and negative LCs doped with a zwitterion Reichardt's dye. The initial homogeneous or homeotropic alignment, as well as the voltage and frequency of the applied electric field, is shown to influence the formation of EC patterns, among which the dynamic scattering mode (DSM) is specially examined for the application as privacy‐protecting smart windows. Using an LC mixture doped with zwitterions, the smart window demonstrates outstanding performance, as well as much improved durability for a wide range of operating conditions. Such a method offers a simple strategy for the fabrication of polymer‐free smart windows.

Thermosolvatochromism of 7H-indolo[1,2-a]quinolinium dyes in pure solvents

Thermosolvatochromism of two dyes generated from hydroxyphenyl and hydroxynaphthyl derivatives of 7H-indolo[1,2-a]quinolinium salts was studied in 14 pure solvents with polarities ranging from 155.3 to 249.5 kJ mol−1 according to ET(30) polarity scale. The measurements were carried out at temperatures ranging from −5 °C to 80 °C. The UV–Vis spectra of both compounds were found to be sensitive to temperature changes. In polar solvents, a decrease in temperature caused a hypsochromic shift in the UV–Vis spectrum of the studied dyes. In less polar solvents, a hypsochromic shift in the UV–Vis spectra of hydroxynaphthyl derivative with decreasing temperature was still observed, but in the spectrum of hydroxyphenyl derivative, a bathochromic shift was recorded. The results were compared with the spectral properties of Reichardt's dye. The influence of temperature on the absorption band position of hydroxynaphthyl derivative in many solvents was even greater than that of Reichardt's dye. The strength of solute-solvent interaction, as well as solvatochromic sensitivity and the type of solvatochromism (positive or negative), which the studied dyes exhibited, were taken into account in order to explain the obtained results. The VBHB model appeared to be very useful for interpretation of thermosolvatochromic properties of the studied dyes.

Hydrostatic Pressure-Induced Spectral Variation of Reichardt's Dye: A Polarity/Pressure Dual Indicator.

The famous solvatochromic Reichardt’s dye was applied to quantify hydrostatic pressure in media. The UV/vis spectra of the dye in various organic solvents are shifted bathochromically or hypsochromically at the shorter- or longer-wavelength band, respectively, upon hydrostatic pressurization. The ET value, determined by an absorption maximum, in ethyl acetate increases from 38.5 kcal mol–1 at 0.1 MPa to 39.2 kcal mol–1 at 300 MPa, which is mostly equal to the one in chloroform at 0.1 MPa. These spectroscopic origins were supported by the time-dependent density functional theory (TD-DFT) calculations. The concept and approach proposed in this paper, i.e., a dual indicator, should attract the attention of a broad spectrum in multidisciplinary science.

Indicator Supraparticles for Smart Gasochromic Sensor Surfaces Reacting Ultrafast and Highly Sensitive

AbstractThe detection of toxic gases, such as NH3 and CO, in the environment is of high interest in chemical, electronic, and automotive industry as even small amounts can display a health risk for workers. Sensors for the real‐time monitoring of these gases should be simple, robust, reversible, highly sensitive, inexpensive and show a fast response. The indicator supraparticles presented herein can fulfill all of these requirements. They consist of silica nanoparticles, which are assembled to supraparticles upon spray‐drying. Sensing molecules such as Reichardt's dye and a binuclear rhodium complex are loaded onto the microparticles to target NH3 and CO detection, respectively. The spray‐drying technique affords high flexibility in primary nanoparticle size selection and thus, easy adjustment of the porosity and specific surface area of the obtained micrometer‐sized supraparticles. This ultimately enables the fine‐tuning of the sensor sensitivity and response. For the application of the indicator supraparticles in a gas detection device, they can be immobilized on a coating. Due to their microscale size, they are large enough to poke out of thin coating layers, thus guaranteeing their gas accessibility, while being small enough to be applicable to flexible substrates.