Deviations from chemical parity (PV) were evaluated with the search for very small enantiomeric excesses in a racemate prepared from non chiral materials and were detected by means of the circular dichroism (CD). Thus, intensely light-absorbing perylenebiscarboximides were attached to axially chiral biphenyls for the amplification of CD effects by exciton interactions of the adjacent chromophores. A rapidly racemising system was applied for the exclusion of artifacts and compared with an analogous with locked chirally. A very slight enantiomeric excess was detected for the (M) enantiomer. Application of the method for other systems was suggested and relations to natural products discussed.
Sofikitis, D., Bougas, L., Katsoprinakis, G.E., Spiliotis, A.K., Loppinet, B. and Rakitzis, T.P. (2014) Evanescent-Wave and Ambient Chiral Sensing by Signal-Reversing Cavity Ringdown Polarimetry. Nature, 514, 76-79. https://doi.org/10.1038/nature13680
Quack, M. (1989) Structure and Dynamics of Chiral Molecules. Angewandte Chemie International Edition, 28, 571-586. https://doi.org/10.1002/anie.198905711
Saleh, N., Zrig, S., Roisnel, T., Guy, L., Bast, R., Saue, T., Darquie, B. and Crassous, J. (2013) A Chiral Rhenium Complex with Predicted High Parity Violation Effects: Synthesis, Stereochemical Characterization by VCD Spectroscopy and Quantum Chemical Calculations. Physical Chemistry Chemical Physics, 15, 10952-10959. https://doi.org/10.1039/c3cp50199j
van’t Hoff, J.H. (1887) La chimie dans l’éspace, Rotterdam. In: Bourgeois, C., Ed., Sur la dissymétrie moléculaire, Collection Epistème, Paris.
Lee, T.D. and Yang, C.N. (1956) Question of Parity Conservation in Weak Interactions. Physical Review Journals Archive, 104, 254-258. https://doi.org/10.1103/PhysRev.104.254
Wu, C.S., Ambler, E., Hayward, R.W., Hoppes, D.D. and Hudson, R.P. (1957) Experimental Test of Parity Conservation in β-Decay. Physical Review Journals Archive, 105, 1413-1415. https://doi.org/10.1103/PhysRev.105.1413
Quack, M. (2002) How Important Is Parity Violation for Molecular and Biomolecular Chirality? Angewandte Chemie International Edition, 41, 4618-4630. https://doi.org/10.1002/anie.200290005
Crassous, J., Monier, F., Dutasta, J.-P., Ziskind, M., Daussy, C., Grain, C. and Chardonnet, C. (2003) Search for Resolution of Chiral Fluorohalogenomethanes and Parity-Violation Effects at the Molecular Level. ChemPhysChem, 4, 541-548. https://doi.org/10.1002/cphc.200200536
Elitzur, A.C. and Shinitzky, M. (2006) P-Violation Manifested at the Molecular Level—A Simple Means for an Absolute Definition of “Left” vs. “Right”. Chemical Abstracts, 144, Article ID: 241270.
Quack, M. and Stohner, J. (2006) Physikalische Chemie 2005. Nachrichten aus der Chemie, 54, 282-291.
Quack, M. (2018) Quantum Dynamics of Chiral Molecules Including Electroweak Parity Violation: From High Resolution Spectroscopy towards Fundamental Symmetries and Asymmetries. 255th ACS National Meeting & Exposition, New Orleans, LA, United States, 18-22 March 2018.
Viglione, R.G. (2004) Theoretical Determination of Parity-Violating Vibrational Frequency Differences between the Enantiomers of Chiral Molecules. The Journal of Chemical Physics, 121, 9959-9963. https://doi.org/10.1063/1.1807815
Quack, M. and Stohner, J. (2003) Combined Multidimensional Anharmonic and Parity Violating Effects in CDBrClF. The Journal of Chemical Physics, 119, 11228-11240. https://doi.org/10.1063/1.1622381
Gottselig, M. and Quack, M. (2005) Steps towards Molecular Parity Violation in Axially Chiral Molecules. I. Theory for Allene and 1,3-Difluoroallene. The Journal of Chemical Physics, 123, Article ID: 084305. https://doi.org/10.1063/1.1884114
Quack, M. and Willeke, M. (2006) Stereomutation Tunneling Switching Dynamics and Parity Violation in Chlorineperoxide Cl-O-O-Cl. The Journal of Physical Chemistry A, 110, 3338-3348. https://doi.org/10.1021/jp055770h
Schwerdtfeger, P., Laerdahl, J.K. and Chardonnet, C. (2002) Calculation of Parity-Violation Effects for the C-F Stretching Mode of Chiral Methyl Fluorides. Physical Review A: Atomic, Molecular, and Optical Physics, 65, Article ID: 042508. https://doi.org/10.1103/PhysRevA.65.042508
Crassous, J., Chardonnet, C., Saue, T. and Schwerdtfeger, P. (2005) Recent Experimental and Theoretical Developments towards the Observation of Parity Violation (PV) Effects in Molecules by Spectroscopy. Organic & Biomolecular Chemistry, 3, 2218-2224. https://doi.org/10.1039/b504212g
Bunker, P.R. and Jensen, P. (2004) Chirality in Rotational Energy Level Clusters. Journal of Molecular Spectroscopy, 228, 640-644. https://doi.org/10.1016/j.jms.2004.02.027
Soulard, P., Asselin, P., Cuisset, A., Aviles, M.J.R.T., Huet, R., Petitprez, D., Demaison, J., Freedman, T.B., Cao, X., Nafie, L.A. and Crassous, J. (2006) Chlorofluoroio-domethane as a Potential Candidate for Parity Violation Measurements. Physical Chemistry Chemical Physics, 8, 79-92. https://doi.org/10.1039/B510675C
Scolnik, Y., Portnaya, I., Cogan, U., Tal, S., Haimovitz, R., Fridkin, M., Elitzur, A.C., Deamer, D.W. and Shinitzky, M. (2006) Subtle Differences in Structural Transitions between Poly-l- and Poly-d-amino Acids of Equal Length in Water. Physical Chemistry Chemical Physics, 8, 333-339. https://doi.org/10.1039/B513974K
MacDermott, A.J.R. and Hegstrom, A. (2004) A Proposed Experiment to Measure the Parity-Violating Energy Difference between Enantiomers from the Optical Rotation of Chiral Ammonia-Like “Cat” Molecules. Chemical Physics, 305, 55-68. https://doi.org/10.1016/j.chemphys.2004.06.017
Kaiser, H., Lindner, J. and Langhals, H. (1991) Synthesis of Nonsymmetrically Substituted Perylene Fluorescent Dyes. Chemische Berichte, 124, 529-535. https://doi.org/10.1002/cber.19911240319
Langhals, H., Karolin, J. and Johansson, L.B.-A. (1998) Spectroscopic Properties of New and Convenient Standards for Measuring Fluorescence Quantum Yields. Journal of the Chemical Society, Faraday Transactions, 94, 2919-2922.
Langhals, H., Demmig, S. and Potrawa, T. (1991) The Relation between Packing Effects and Solid State Fluorescence of Dyes. Journal für Praktische Chemie, 333, 733-748. https://doi.org/10.1002/prac.19913330508
Nakanishi, K. and Berova, N. (1994) The Excitation Chirality Method (Circular Dichroism. Principles and Their Applications). VCH Verlagsgesellschaft, Weinheim.
Wolf, C., Koenig, W.A. and Roussel, C. (1995) Conversion of a Racemate into a Single Enantiomer in One Step by Chiral Liquid Chromatography: Studies with Rac-2,2’-diiodobiphenyl. Chirality, 7, 610-611.
Jung, M., Fluck, M. and Schurig, V. (1994) Enantiomerization of 2,2’-diisopropylbiphenyl during Chiral Inclusion Gas Chromatography: Determination of the Rotational Energy Barrier by Computer Simulation of Dynamic Chromatographic Elution Profiles. Chirality, 6, 510-512.
Hammerschmidt, E. and Voegtle, F. (1980) Internal Mobility of Open-Chain Oligophenyl Compounds. Chemische Berichte, 113, 1121-1124.
Charton, M. (1977) Steric Effects. 8. Racemization of Chiral Biphenyls. The Journal of Organic Chemistry, 42, 2528-2529.
Kuhn, R. and Albrecht, O. (1927) Stereochemistry of Aromatic Compounds. IV. Racemization of Optically Active Diphenic Acids and the Oscillation of the Benzine Nucleus in the Diphenyl System. Liebigs Annalen der Chemie, 455, 272-299.
Prelog, V. and Helmchen, G. (1982) Bases of the CIP System and Proposal for a Revision. Angewandte Chemie, 94, 614-631. https://doi.org/10.1002/anie.198205671
Cook, D.E. and Turner, E.E. (1937) Racemization of Some d-o-(2-Dimethyla-minophenyl)Phenyltrimethylammonium Salts. Journal of the Chemical Society, 88-89.
Adams, R. and Snyder, H.R. (1938) Stereochemistry of Biphenyls. XLIII. Effect of Substituents in the 4-Position of 2-Nitro-6-Carboxy-2’-Methylbiphenyl. Journal of the American Chemical Society, 60, 1411-1415.
Adams, R. and Hale, J.B. (1939) Stereochemistry of Biphenyls. XLVIII. Comparison of the Racemization Rates of Three Isomeric 2,2’,6-nitro-, carboxy-, Methyl-Biphenyls. Journal of the American Chemical Society, 61, 2825-2828.
Bell, F. and Robinson, P.H. (1927) Diphenyl Series. VII. The Relative Stability of Optically Active Diphenic Acids. Journal of the Chemical Society, 2234-2239.
Theilacker, W. and Boehn, H. (1967) Optically Active 2,2’-Dimethylbiphenyl, the Simplest Atropisomeric Hydrocarbon. Angewandte Chemie International Edition, 6, 251.
Langhals, H. (2005) Control of the Interactions in Multichromophores: Novel Concepts. Perylene Bis-Imides as Components for Larger Functional Units. Helvetica Chimica Acta, 88, 1309-1343. https://doi.org/10.1002/hlca.200590107
Langhals, H. (1995) Cyclic Carboxylic Imide Structures as Structure Elements of High Stability. Novel Developments in Perylene Dye Chemistry. Heterocycles, 40, 477-500. https://doi.org/10.3987/REV-94-SR2
Nakamura, S., Murakami, A., Adachi, M. and Irie, M. (1996) A New Guiding Principle towards the Spectral Design of Organic Functional Molecules. Pure and Applied Chemistry, 68, 1441-1442. https://doi.org/10.1351/pac199668071441
Johansson, L.B.-A. and Langhals, H. (1991) Spectroscopic Studies of Fluorescent Perylene Dyes. Spectrochimica Acta, 47A, 857-861. https://doi.org/10.1016/0584-8539(91)80272-K
Langhals, H. (1985) Synthesis of Highly Pure Perylene Fluorescent Dyes in Large Scale Amounts—Specific Preparation of Atropic Isomers. Chemische Berichte, 118, 4641-4645. https://doi.org/10.1002/cber.19851181138
Demmig, S. and Langhals, H. (1988) Readily Soluble Lightfast Perylene Dyes. Chemische Berichte, 121, 225-230. https://doi.org/10.1002/cber.19881210205
Langhals, H., Hofer, A., Bernhard, S., Siegel, J.S. and Mayer, P. (2011) Axially Chiral Bichromophoric Fluorescent Dyes. The Journal of Organic Chemistry, 76, 990-992. https://doi.org/10.1021/jo102254a
Langhals, H. and Gold, J. (1997) Chiral Bifluorophoric Perylene Dyes with Unusually High CD Effects. A Simple Model for the Photosynthesis Reaction Center. Liebigs Annalen, 1151-1153. https://doi.org/10.1002/jlac.199719970615