60 Years of Betaine 30─From Solvatochromic Discovery to Future Frontiers.

Betaine-30 (B30) was reported by Karl Dimroth and Christian Reichardt et al. in 1963 as a solvatochromic probe that can be easily synthesized, shows good solubility, and remains stable in various organic solvents and solutions. Its strongly negatively solvatochromic behavior arises from differential solvation between its electronic ground and excited states, making it a valuable tool for assessing solvent polarity using the ET(30) polarity scale, also devised by Dimroth and Reichardt. In addition, advancements in femtosecond laser spectroscopy in the 1990s greatly improved the understanding of B30's relaxation dynamics following photoexcitation. In solvents capable of hydrogen bonding, such as alcohols, intermolecular hydrogen-bond rearrangement contributes to the multiple relaxation components observed. Since the 1990s, the applications of B30 have expanded beyond simple organic solvents to include complex solvent mixtures, such as electrolyte solutions for battery technologies and eutectic solvent mixtures. Given the growing importance of these complex solvent mixtures, B30 is becoming an increasingly valuable tool for studying previously unexplored solvation 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.