60 Years of Betaine 30–From Solvatochromic Discovery to Future Frontiers

Pandian, Rathiesh; Burda, Henrik; Alfurayj, Ibrahim; Reichardt, Christian; Burda, Clemens

doi:10.1021/acs.jpcb.4c02813

60 Years of Betaine 30–From Solvatochromic Discovery to Future Frontiers

Journal Article · Thu Jul 11 00:00:00 EDT 2024 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.4c02813· OSTI ID:2548175

Pandian, Rathiesh ^[1]; ^[1]; ^[2]; Reichardt, Christian ^[3]; ^[1]

Case Western Reserve University, Cleveland, OH (United States)
Case Western Reserve University, Cleveland, OH (United States); King Faisal University, Al-Ahsa (Saudi Arabia)
Philipps-University of Marburg (Germany)

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 E_T(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. Furthermore, given the growing importance of these complex solvent mixtures, B30 is becoming an increasingly valuable tool for studying previously unexplored solvation properties.

View Accepted Manuscript (DOE)

Research Organization:: Case Western Reserve University, Cleveland, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019409

OSTI ID:: 2548175

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 29 Vol. 128; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

Syntheses and UV/Vis-Spectroscopic Properties of Hydrophilic 2-, 3-, and 4-Pyridyl-Substituted Solvatochromic and Halochromic PyridiniumN-Phenolate Betaine Dyes as New Empirical Solvent Polarity Indicators Reichardt, Christian; Che, Daqing; Heckenkemper, Guido European Journal of Organic Chemistry, Vol. 2001, Issue 12 https://doi.org/10.1002/1099-0690(200106)2001:12<2343::AID-EJOC2343>3.0.CO;2-I	journal	June 2001
An Examination of Linear Solvation Energy Relationships Kamlet, M. J.; Abboud, J. L. M.; Taft, R. W. Progress in Physical Organic Chemistry https://doi.org/10.1002/9780470171929.ch6	book	January 2007
Beziehungen zwischen den Absorptionsspektren im Ultraviolett und der Konstitution organischer Verbindungen Dimroth, Karl Angewandte Chemie, Vol. 52, Issue 34 https://doi.org/10.1002/ange.19390523402	journal	August 1939
Die Anwendung der Solvatochromie organischer Farbstoffe zur kolorimetrischen Analyse von Lösungsmittel‐ und insbesondere von Treibstoffgemischen John, Walter Angewandte Chemie, Vol. 59, Issue 7-8 https://doi.org/10.1002/ange.19470590702	journal	July 1947
Empirische Parameter der Lösungsmittelpolarität Reichardt, Chr. Angewandte Chemie, Vol. 77, Issue 1 https://doi.org/10.1002/ange.19650770105	journal	January 1965
Empirical Parameters of the Polarity of Solvents Reichardt, C. Angewandte Chemie International Edition in English, Vol. 4, Issue 1 https://doi.org/10.1002/anie.196500291	journal	January 1965
Über Mesomerie bei N‐Oxyphenyl‐pyridinium‐Basen Schneider, Wilhelm; Döbling, Walter; Cordua, Ruth Berichte der deutschen chemischen Gesellschaft (A and B Series), Vol. 70, Issue 8 https://doi.org/10.1002/cber.19370700802	journal	August 1937
How Many Molecular Layers of Polar Solvent Molecules Control Chemistry? The Concept of Compensating Dipoles Langhals, Heinz; Braun, Patricia; Dietl, Christian Chemistry – A European Journal, Vol. 19, Issue 40 https://doi.org/10.1002/chem.201300770	journal	August 2013
Über Pyridinium-N-phenol-betaine und ihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln Dimroth, Karl; Reichardt, Christian; Siepmann, Theodor Justus Liebigs Annalen der Chemie, Vol. 661, Issue 1 https://doi.org/10.1002/jlac.19636610102	journal	February 1963
Über Pyridinium‐N‐phenolat‐Betaine und ihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln, X. Erweiterung, Korrektur und Neudefinition der E_T‐Lösungsmittelpolaritätsskala mit Hilfe eines lipophilen penta‐tert‐butyl‐substituierten Pyridinium‐N‐phenolat‐Betainfarbstoffes Reichardt, Christian; Harbusch‐Görnert, Erwin Liebigs Annalen der Chemie, Vol. 1983, Issue 5 https://doi.org/10.1002/jlac.198319830502	journal	May 1983
Über Pyridinium‐N‐phenolat‐Betaine und ihre Verwendung zur Charakterisierung der Polarität von Lösungsmitteln, XI. Herstellung und UV/VIS‐spektroskopische Eigenschaften eines wasserlöslichen Carboxylat‐substituierten Pyridinium‐N‐phenolat‐Betainfarbstoffs Reichardt, Christian; Harbusch‐Görnert, Erwin; SchWäfer, Gerhard Liebigs Annalen der Chemie, Vol. 1988, Issue 9 https://doi.org/10.1002/jlac.198819880904	journal	September 1988
Solvent polarity scales: determination of new E _T (30) values for 84 organic solvents: SOLVENT POLARITY SCALES Cerón-Carrasco, José P.; Jacquemin, Denis; Laurence, Christian Journal of Physical Organic Chemistry, Vol. 27, Issue 6 https://doi.org/10.1002/poc.3293	journal	February 2014
Determination of empirical parameters of solvent polarity E T in binary mixtures by solvatochromic pyridinium-N-phenol betaine dyes Maksimović, Z. B.; Reichardt, C.; Spirić, A. Fresenius' Zeitschrift für Analytische Chemie, Vol. 270, Issue 2 https://doi.org/10.1007/BF00434059	journal	January 1974
Specific excitation of the solvent coordinate in the S3→S1 and S1→S0 radiationless decay of the betaines Levinger, Nancy E.; Johnson, Alan E.; Walker, Gilbert C. Chemical Physics Letters, Vol. 196, Issue 1-2 https://doi.org/10.1016/0009-2614(92)85947-9	journal	August 1992
Evidence for intermolecular hydrogen-bond rearrangement in the electron transfer dynamics of betaine-30 in n-butanol Reid, Philip J.; Alex, Simson; Jarzeba, Wlodzimierz Chemical Physics Letters, Vol. 229, Issue 1-2 https://doi.org/10.1016/0009-2614(94)01017-X	journal	October 1994
ET(33), a solvatochromic polarity and micellar probe for neutral aqueous solutions Kessler, Manfred A.; Wolfbeis, Otto S. Chemistry and Physics of Lipids, Vol. 50, Issue 1 https://doi.org/10.1016/0009-3084(89)90025-X	journal	April 1989
Experimental and theoretical study of inhomogeneous electron transfer in betaine: comparisons of measured and predicted spectral dynamics Johnson, Alan E.; Levinger, Nancy E.; Jarzȩba, Włodzimierz Chemical Physics, Vol. 176, Issue 2-3 https://doi.org/10.1016/0301-0104(93)80261-7	journal	October 1993
An attenuated total internal reflectance spectroscopy study of ET(30) at the free oil-water interface Perera, Jilska M.; Stevens, Geoffrey W.; Grieser, Franz Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 95, Issue 2-3 https://doi.org/10.1016/0927-7757(94)03018-U	journal	February 1995
Luminescence of Reichardt's dye in polyelectrolyte-modified saponite colloids Pribus, Marek; Budzák, Šimon; Slušná, Lenka Pribusová Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 642 https://doi.org/10.1016/j.colsurfa.2022.128663	journal	June 2022
Solvation dynamics of room-temperature ionic liquids: evidence for collective solvent motion on sub-picosecond timescales Kobrak, Mark N.; Znamenskiy, Vasiliy Chemical Physics Letters, Vol. 395, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.07.049	journal	September 2004
Hydrodynamic voltammetry of Fe2+/3+ in aqueous deep eutectic solvents towards redox flow batteries Prado, Desiree Mae; Shen, Xiaochen; Savinell, Robert Electrochimica Acta, Vol. 467 https://doi.org/10.1016/j.electacta.2023.143082	journal	November 2023
Physicochemical properties of choline chloride-based deep eutectic solvents and excess properties of their pseudo-binary mixtures with 1-butanol Gajardo-Parra, Nicolás F.; Lubben, Michael J.; Winnert, Joshua M. The Journal of Chemical Thermodynamics, Vol. 133 https://doi.org/10.1016/j.jct.2019.02.010	journal	June 2019
Choline Fluoride-Ethylene glycol deep eutectic solvent mixture – Synthesis and physicochemical properties Alfurayj, Ibrahim; Pandian, Rathiesh; Springer, Sarah Journal of Molecular Liquids, Vol. 386 https://doi.org/10.1016/j.molliq.2023.122454	journal	September 2023
Solvation dynamics of choline fluoride in ethylene glycol – Water mixtures Alfurayj, Ibrahim; Cecilia Fraenza, Carla; Pandian, Rathiesh Journal of Molecular Liquids, Vol. 392 https://doi.org/10.1016/j.molliq.2023.123448	journal	December 2023
Chain length and OH-spacing effects on diol-based deep eutectic solvents Pandian, Rathiesh; Kim, Daniel; Zhang, Yong Journal of Molecular Liquids, Vol. 393 https://doi.org/10.1016/j.molliq.2023.123534 123534	journal	January 2024
Deep Eutectic Solvents: A Review of Fundamentals and Applications Hansen, Benworth B.; Spittle, Stephanie; Chen, Brian Chemical Reviews, Vol. 121, Issue 3 https://doi.org/10.1021/acs.chemrev.0c00385	journal	December 2020
Thermodynamic Study of Choline Chloride-Based Deep Eutectic Solvents with Water and Methanol Wang, Yanxin; Ma, Chunyan; Liu, Chang Journal of Chemical & Engineering Data, Vol. 65, Issue 5 https://doi.org/10.1021/acs.jced.9b01113	journal	May 2020
Solvation Effects in Organic Chemistry: A Short Historical Overview Reichardt, Christian The Journal of Organic Chemistry, Vol. 87, Issue 3 https://doi.org/10.1021/acs.joc.1c01979	journal	November 2021
Solvation Dynamics of Wet Ethaline: Water is the Magic Component Alfurayj, Ibrahim; Fraenza, Carla Cecilia; Zhang, Yong The Journal of Physical Chemistry B, Vol. 125, Issue 31 https://doi.org/10.1021/acs.jpcb.1c04629	journal	August 2021
Unusual Hydration Properties of Choline Fluoride-Based Deep Eutectic Solvents Alfurayj, Ibrahim; Prado, Desiree Mae; Prado, Ross Clark The Journal of Physical Chemistry B, Vol. 128, Issue 11, p. 2762-2772 https://doi.org/10.1021/acs.jpcb.3c07625	journal	March 2024
Entropy–Enthalpy Compensation in Electron-Transfer Processes Burda, Henrik; Hsieh, Isabelle; Burda, Clemens The Journal of Physical Chemistry Letters, Vol. 15, Issue 14 https://doi.org/10.1021/acs.jpclett.4c00734	journal	April 2024
Fate of a Deep Eutectic Solvent upon Cosolvent Addition: Choline Chloride–Sesamol 1:3 Mixtures with Methanol Busato, Matteo; Del Giudice, Alessandra; Di Lisio, Valerio ACS Sustainable Chemistry & Engineering, Vol. 9, Issue 36 https://doi.org/10.1021/acssuschemeng.1c03809	journal	September 2021
Solvatochromic Dyes as Solvent Polarity Indicators Reichardt, Christian Chemical Reviews, Vol. 94, Issue 8 https://doi.org/10.1021/cr00032a005	journal	December 1994
Deep Eutectic Solvents (DESs) and Their Applications Smith, Emma L.; Abbott, Andrew P.; Ryder, Karl S. Chemical Reviews, Vol. 114, Issue 21 https://doi.org/10.1021/cr300162p	journal	October 2014
Pyridinium N-Phenolate Betaine Dyes Machado, Vanderlei G.; Stock, Rafaela I.; Reichardt, Christian Chemical Reviews, Vol. 114, Issue 20 https://doi.org/10.1021/cr5001157	journal	September 2014
Dynamic Solvent Effect on Betaine-30 Electron-Transfer Kinetics in Alcohols Reid, Philip J.; Barbara, Paul F. The Journal of Physical Chemistry, Vol. 99, Issue 11 https://doi.org/10.1021/j100011a024	journal	March 1995
Interplay of solvent motion and vibrational excitation in electron-transfer kinetics: experiment and theory Walker, Gilbert C.; Aakesson, Eva; Johnson, Alan E. The Journal of Physical Chemistry, Vol. 96, Issue 9 https://doi.org/10.1021/j100188a032	journal	April 1992
Investigation of micelles, microemulsions, and phospholipid bilayers with the pyridinium-N-phenolbetaine ET(30), a polarity probe for aqueous interfaces Zachariasse, Klaas A.; Kozankiewicz, Boleslaw The Journal of Physical Chemistry, Vol. 85, Issue 18 https://doi.org/10.1021/j150618a022	journal	September 1981
The solvatochromic comparison method. 6. The .pi.* scale of solvent polarities Kamlet, Mortimer J.; Abboud, Jose Luis; Taft, R. W. Journal of the American Chemical Society, Vol. 99, Issue 18 https://doi.org/10.1021/ja00460a031	journal	August 1977
The Effect of Solvent on Spectra. I. A New Empirical Measure of Solvent Polarity: Z-Values Kosower, Edward M. Journal of the American Chemical Society, Vol. 80, Issue 13 https://doi.org/10.1021/ja01546a020	journal	July 1958
Kemp Elimination in Membrane Mimetic Reaction Media: Probing Catalytic Properties of Catanionic Vesicles Formed from Double-Tailed Amphiphiles Klijn, Jaap E.; Engberts, Jan B. F. N. Journal of the American Chemical Society, Vol. 125, Issue 7 https://doi.org/10.1021/ja027772a	journal	January 2003
Deep Eutectic Solvents Formed between Choline Chloride and Carboxylic Acids: Versatile Alternatives to Ionic Liquids Abbott, Andrew P.; Boothby, David; Capper, Glen Journal of the American Chemical Society, Vol. 126, Issue 29 https://doi.org/10.1021/ja048266j	journal	July 2004
Describing Chemical Reactivity with Frontier Molecular Orbitalets Yu, Jincheng; Su, Neil Qiang; Yang, Weitao JACS Au, Vol. 2, Issue 6 https://doi.org/10.1021/jacsau.2c00085	journal	June 2022
Enhanced Dynamics and Charge Transport at the Eutectic Point: A New Paradigm for the Use of Deep Eutectic Solvent Systems Spittle, Stephanie; Alfurayj, Ibrahim; Hansen, Benworth Bryce JACS Au, Vol. 3, Issue 11 https://doi.org/10.1021/jacsau.3c00420	journal	November 2023
Linear solvation energy relationships. 23. A comprehensive collection of the solvatochromic parameters, .pi.*, .alpha., and .beta., and some methods for simplifying the generalized solvatochromic equation Kamlet, Mortimer J.; Abboud, Jose Luis M.; Abraham, Michael H. The Journal of Organic Chemistry, Vol. 48, Issue 17 https://doi.org/10.1021/jo00165a018	journal	August 1983
Measuring Intramolecular Charge Transfer via Coherent Generation of THz Radiation Beard, Matthew C.; Turner, Gordon M.; Schmuttenmaer, Charles A. The Journal of Physical Chemistry A, Vol. 106, Issue 6 https://doi.org/10.1021/jp013603l	journal	February 2002
Molecular Dynamics Study of Polarity in Room-Temperature Ionic Liquids Znamenskiy, Vasiliy; Kobrak, Mark N. The Journal of Physical Chemistry B, Vol. 108, Issue 3 https://doi.org/10.1021/jp035891m	journal	December 2003
Experimental and Theoretical Study of Excited-State Structure and Relaxation Processes of Betaine-30 and of Pyridinium Model Compounds Kharlanov, V.; Rettig, W. The Journal of Physical Chemistry A, Vol. 113, Issue 40 https://doi.org/10.1021/jp904537k	journal	September 2009
Computer Simulations of the Solvatochromism of Betaine-30 Mente, S. R.; Maroncelli, M. The Journal of Physical Chemistry B, Vol. 103, Issue 36 https://doi.org/10.1021/jp991549r	journal	September 1999
Solvent and Intramolecular Effects on the Absorption Spectrum of Betaine-30 Lobaugh, John; Rossky, Peter J. The Journal of Physical Chemistry A, Vol. 104, Issue 5 https://doi.org/10.1021/jp993444u	journal	February 2000
Evolution of microscopic heterogeneity and dynamics in choline chloride-based deep eutectic solvents Spittle, Stephanie; Poe, Derrick; Doherty, Brian Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-021-27842-z	journal	January 2022
Solvatomorphism of Reichardt's dye Pike, Sarah J.; Bond, Andrew D.; Hunter, Christopher A. CrystEngComm, Vol. 20, Issue 21 https://doi.org/10.1039/C8CE00480C	journal	January 2018
The use of Reichardt's dye as an indicator of surface polarity Macquarrie, Duncan J.; Tavener, Stewart J.; Gray, Gary W. New Journal of Chemistry, Vol. 23, Issue 7 https://doi.org/10.1039/a901563i	journal	January 1999
Temperature-dependent microscopic solvent properties of ‘dry’ and ‘wet’ 1-butyl-3-methylimidazolium hexafluorophosphate: correlation with ET(30) and Kamlet–Taft polarity scales Baker, Sheila N.; Baker, Gary A.; Bright, Frank V. Green Chemistry, Vol. 4, Issue 2 https://doi.org/10.1039/b111285f	journal	March 2002
Novel solvent properties of choline chloride/urea mixturesElectronic supplementary information (ESI) available: spectroscopic data. See http://www.rsc.org/suppdata/cc/b2/b210714g/ Abbott, Andrew P.; Capper, Glen; Davies, David L. Chemical Communications, Issue 1 https://doi.org/10.1039/b210714g	journal	November 2002
Polarity of ionic liquids determined empirically by means of solvatochromic pyridinium N-phenolate betaine dyes Reichardt, Christian Green Chemistry, Vol. 7, Issue 5 https://doi.org/10.1039/b500106b	journal	January 2005
Solvatochromism, thermochromism, piezochromism, halochromism, and chiro-solvatochromism of pyridinium N-phenoxide betaine dyes Reichardt, C. Chemical Society Reviews, Vol. 21, Issue 3 https://doi.org/10.1039/cs9922100147	journal	January 1992
The properties of organic liquids that are relevant to their use as solvating solvents Marcus, Y. Chemical Society Reviews, Vol. 22, Issue 6 https://doi.org/10.1039/cs9932200409	journal	January 1993
Dynamical effects in electron transfer reactions Sumi, H.; Marcus, R. A. The Journal of Chemical Physics, Vol. 84, Issue 9 https://doi.org/10.1063/1.449978	journal	May 1986
Intramolecular vibrational excitations accompanying solvent‐controlled electron transfer reactions Jortner, Joshua; Bixon, Mordechai The Journal of Chemical Physics, Vol. 88, Issue 1 https://doi.org/10.1063/1.454632	journal	January 1988
Dynamic solvent effects on electron transfer rates in the inverted regime: Ultrafast studies on the betaines Åkesson, Eva; Walker, Gilbert C.; Barbara, Paul F. The Journal of Chemical Physics, Vol. 95, Issue 6 https://doi.org/10.1063/1.460774	journal	September 1991
Temperature dependence of the inverted regime electron transfer kinetics of betaine‐30 and the role of molecular modes Åkesson, Eva; Johnson, Alan E.; Levinger, Nancy E. The Journal of Chemical Physics, Vol. 96, Issue 10 https://doi.org/10.1063/1.462384	journal	May 1992
Calculated solvent reorganization entropies, free energies, and fluctuations of the energy gaps for intramolecular electron transfer and excitation of the solvatochromic dye B30 Parson, William W.; Burda, Clemens The Journal of Chemical Physics, Vol. 159, Issue 15 https://doi.org/10.1063/5.0164136	journal	October 2023
Temperature-dependent solvent reorganization entropies, free energies, and transition dipole strengths for the photoexcitation of Reichardt’s dye B30 Echelberry, Kevin; Burda, Henrik; Willis, Preston The Journal of Chemical Physics, Vol. 159, Issue 15 https://doi.org/10.1063/5.0164142	journal	October 2023
Ultrafast experiments on the role of vibrational modes in electron transfer Johnson, A. E.; Levinger, N. E.; Kliner, D. A. V. Pure and Applied Chemistry, Vol. 64, Issue 9 https://doi.org/10.1351/pac199264091219	journal	January 1992
Pyridinium N-phenolate betaine dyes as empirical indicators of solvent polarity: Some new findings Reichardt, C. Pure and Applied Chemistry, Vol. 76, Issue 10 https://doi.org/10.1351/pac200476101903	journal	January 2004
A Comprehensive Review on Deep Eutectic Solvents and Its Use to Extract Bioactive Compounds of Pharmaceutical Interest Ferreira, Cátia; Sarraguça, Mafalda Pharmaceuticals, Vol. 17, Issue 1 https://doi.org/10.3390/ph17010124	journal	January 2024
Ionic Liquid-Based Electrolytes for Energy Storage Devices: A Brief Review on Their Limits and Applications Karuppasamy, K.; Theerthagiri, Jayaraman; Vikraman, Dhanasekaran Polymers, Vol. 12, Issue 4 https://doi.org/10.3390/polym12040918	journal	April 2020