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  • Review Article
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Circularly polarized lanthanide luminescence for advanced security inks

Abstract

Authenticating products and documents with security inks is vital to global commerce, security and health. Lanthanide complexes are widely used in luminescent security inks owing to their unique and robust photophysical properties. Lanthanide complexes can also be engineered to undergo circularly polarized luminescence (CPL), which encodes chiral molecular fingerprints in luminescence spectra that cannot be decoded by conventional optical measurements. However, chiral CPL signals have not yet been exploited as an extra security layer in advanced security inks. This Review introduces CPL and related concepts that are necessary to appreciate the challenges and potential of lanthanide-based, CPL-active security inks. We describe recent advances in CPL analysis and read-out technologies that have expedited CPL-active security ink applications. Further, we provide a systematic meta-analysis of strongly CPL-active Euiii, Tbiii, Smiii, Ybiii, Cmiii, Dyiii and Criii complexes, discussing the suitability of their photophysical properties and highlighting promising candidates. We conclude by providing key recommendations for the development and advancement of the field.

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Fig. 1: Security inks featuring long-lived lanthanide luminescence and rapidly emitting organic fluorophores.
Fig. 2: Circularly polarized light and enantioselective image contrast.
Fig. 3: A subset of chiral lanthanide complexes discussed as candidates for CPL-active security inks.
Fig. 4: Next-generation CPL spectrometers have time-gated detection and improved signal-to-noise ratio relative to legacy CPL spectrometers.
Fig. 5: Reported gem values for CPL-active lanthanide and Criii complexes discussed here.
Fig. 6: Relative proportion of Euiii gem values reported in the literature for each emission band.

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References

  1. Andres, J., Hersch, R. D., Moser, J. E. & Chauvin, A. S. A new anti-counterfeiting feature relying on invisible luminescent full color images printed with lanthanide-based inks. Adv. Funct. Mater. 24, 5029–5036 (2014). Demonstrated that Lniii luminescence can afford full-colour images that are otherwise invisible under room light.

    Article  CAS  Google Scholar 

  2. Lowe, P. Counterfeiting: links to organised crime and terrorist funding. J. Financ. Crime 13, 255–257 (2006).

    Article  Google Scholar 

  3. Soon, J. M. & Manning, L. Developing anti-counterfeiting measures: the role of smart packaging. Food Res. Int. 123, 135–143 (2019).

    Article  PubMed  Google Scholar 

  4. Sonnex, E., Almond, M. J., Baum, J. V. & Bond, J. W. Identification of forged Bank of England £20 banknotes using IR spectroscopy. Spectrochim. Acta A Mol. Biomol. Spectrosc. 118, 1158–1163 (2014).

    Article  CAS  PubMed  Google Scholar 

  5. Lau, Y. B., Ar, O. B. N., Anein, Y. H. & Oag, A. B. Meta-hologram-based authentication scheme employing a speckle pattern fingerprint. Opt. Express 28, 8924–8936 (2020).

    Article  Google Scholar 

  6. Prime, E. L. & Solomon, D. H. Australia’s plastic banknotes: fighting counterfeit currency. Angew. Chem. Int. Ed. 49, 3726–3736 (2010).

    Article  CAS  Google Scholar 

  7. Lancaster, I. M. & Mitchell, A. The growth of optically variable features on banknotes. Proc. SPIE 5310, 34–45 (2004).

    Article  Google Scholar 

  8. Baek, S., Choi, E., Baek, Y. & Lee, C. Detection of counterfeit banknotes using multispectral images. Digit. Signal. Process. 78, 294–304 (2018).

    Article  Google Scholar 

  9. Zheng, Y. et al. Unclonable plasmonic security labels achieved by shadow-mask-lithography-assisted self-assembly. Adv. Mater. 28, 2330–2336 (2016).

    Article  CAS  PubMed  Google Scholar 

  10. Yeh, C.-H., Sung, P.-Y., Kuo, C.-H. & Yeh, R.-N. Robust laser speckle recognition system for authenticity identification. Opt. Express 20, 24382–24393 (2012).

    Article  PubMed  Google Scholar 

  11. Carro-Temboury, M. R., Arppe, R., Vosch, T. & Sørensen, T. J. An optical authentication system based on imaging of excitation-selected lanthanide luminescence. Sci. Adv. 4, e1701384 (2018).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  12. Arppe, R. & Sørensen, T. J. Physical unclonable functions generated through chemical methods for anti-counterfeiting. Nat. Rev. Chem. 1, 0031 (2017). An excellent introduction to anti-counterfeiting technologies.

    Article  CAS  Google Scholar 

  13. Martins, A. R., Talhavini, M., Vieira, M. L., Zacca, J. J. & Braga, J. W. B. Discrimination of whisky brands and counterfeit identification by UV–Vis spectroscopy and multivariate data analysis. Food Chem. 229, 142–151 (2017).

    Article  CAS  PubMed  Google Scholar 

  14. de Almeida, M. R., Correa, D. N., Rocha, W. F. C., Scafi, F. J. O. & Poppi, R. J. Discrimination between authentic and counterfeit banknotes using Raman spectroscopy and PLS-DA with uncertainty estimation. Microchem. J. 109, 170–177 (2013).

    Article  CAS  Google Scholar 

  15. Guedes, A. et al. Raman microspectroscopy of genuine and fake euro banknotes. Spectrosc. Lett. 46, 569–576 (2013).

    Article  CAS  Google Scholar 

  16. Imperio, E., Calò, E., Valli, L. & Giancane, G. Spectral investigations on 1000 £ banknotes throughout Italian Republic. Vib. Spectrosc. 79, 52–58 (2015).

    Article  CAS  Google Scholar 

  17. Novais Rodrigues, A. R., Melquiades, F. L., Appoloni, C. R. & Marques, E. N. Characterization of Brazilian banknotes using portable X-ray fluorescence and Raman spectroscopy. Forensic Sci. Int. 302, 109872 (2019).

    Article  CAS  PubMed  Google Scholar 

  18. Li, H. et al. The design of room-temperature-phosphorescent carbon dots and their application as a security ink. J. Mater. Chem. C 7, 10605–10612 (2019).

    Article  CAS  Google Scholar 

  19. Kalytchuk, S., Wang, Y., Poláková, K. & Zbořil, R. Carbon dot fluorescence-lifetime-encoded anti-counterfeiting. ACS Appl. Mater. Interfaces 10, 29902–29908 (2018).

    Article  CAS  PubMed  Google Scholar 

  20. Hartl, A., Grubert, J., Schmalstieg, D. & Reitmayr, G. in Proceedings of the 2013 IEEE International Symposium on Mixed and Augmented Reality (ISMAR) 75–82 (IEEE, 2013).

  21. Kumar, P., Dwivedi, J. & Gupta, B. K. Highly luminescent dual mode rare-earth nanorod assisted multi-stage excitable security ink for anti-counterfeiting applications. J. Mater. Chem. C 2, 10468–10475 (2014).

    Article  CAS  Google Scholar 

  22. Singh, A. K., Singh, S. & Gupta, B. K. Highly efficient, chemically stable, and UV/blue-light-excitable biluminescent security ink to combat counterfeiting. ACS Appl. Mater. Interfaces 10, 44570–44575 (2018).

    Article  CAS  PubMed  Google Scholar 

  23. Štolc, S., Wild, P., Valentin, K., Daubner, F. & Clabian, M. in Proceedings of the 2016 European Intelligence and Security Informatics Conference (EISIC) 9–15 (IEEE, 2017).

  24. Valentín, K., Wild, P., Štolc, S., Daubner, F. & Clabian, M. Optical benchmarking of security document readers for automated border control. Proc SPIE 9995, 999503 (2016).

    Google Scholar 

  25. Tian, Z. et al. Conjugated polymer nanoparticles incorporating antifade additives for improved brightness and photostability. J. Phys. Chem. B 117, 4517–4520 (2013).

    Article  CAS  PubMed  Google Scholar 

  26. Belair, S. D., Maupin, C. L., Logue, M. W. & Riehl, J. P. Analysis of the temperature dependence of the racemization of Eu(iii) complexes through measurement of steady-state circularly polarized luminescence. J. Lumin. 86, 61–66 (2000). Demonstrated that enantiopure Euiii complexes can be resistant towards thermal racemization, a necessary aspect for anti-counterfeiting applications.

    Article  CAS  Google Scholar 

  27. Frawley, A. T., Pal, R. & Parker, D. Very bright, enantiopure europium(iii) complexes allow time-gated chiral contrast imaging. Chem. Commun. 52, 13349–13352 (2016). Describes enantioselective CPL epifluorescence microscopy of a Euiii complex impregnated onto a paper substrate.

    Article  CAS  Google Scholar 

  28. Mahesh, S., Lekshmi, C. L., Renuka, K. D. & Joseph, K. Simple and cost-effective synthesis of fluorescent graphene quantum dots from honey: application as stable security ink and white-light emission. Part. Part. Syst. Charact. 33, 70–74 (2016).

    Article  CAS  Google Scholar 

  29. Zinna, F. & Di Bari, L. in Lanthanide-Based Multifunctional Materials (eds Martin-Ramos, P. & Ramos-Silva, M.) 171–194 (Elsevier, 2018).

  30. Piguet, C. Set aside when building the periodic table 150 years ago, are rare earths any better considered by chemists in the 21st century? Chimia 73, 165–172 (2019).

    Article  CAS  PubMed  Google Scholar 

  31. Binnemans, K. Interpretation of europium(iii) spectra. Coord. Chem. Rev. 295, 1–45 (2015).

    Article  CAS  Google Scholar 

  32. Friedman, H. G., Choppin, G. R. & Feuerbacher, D. G. The shapes of the f orbitals. J. Chem. Educ. 41, 354–358 (1964). An excellent introduction to f orbitals, which are essential to the photophysics of lanthanide complexes.

    Article  CAS  Google Scholar 

  33. Bünzli, J. C. G. Rising stars in science and technology: luminescent lanthanide materials. Eur. J. Inorg. Chem. 2017, 5058–5063 (2017).

    Article  CAS  Google Scholar 

  34. Van Vleck, J. H. The puzzle of rare-earth spectra in solids. J. Phys. Chem. 41, 67–80 (1937).

    Article  Google Scholar 

  35. Bünzli, J. C. G. & Eliseeva, S. V. Intriguing aspects of lanthanide luminescence. Chem. Sci. 4, 1939–1949 (2013).

    Article  CAS  Google Scholar 

  36. Butler, S. J. et al. EuroTracker dyes: highly emissive europium complexes as alternative organelle stains for live cell imaging. Chem. Sci. 5, 1750–1756 (2014).

    Article  CAS  Google Scholar 

  37. Muller, G. Luminescent chiral lanthanide(iii) complexes as potential molecular probes. Dalton Trans. 44, 9692–9707 (2009).

    Article  CAS  Google Scholar 

  38. Krasnoperov, L. N., Marras, S. A. E., Kozlov, M., Wirpsza, L. & Mustaev, A. Luminescent probes for ultrasensitive detection of nucleic acids. Bioconjug. Chem. 21, 319–327 (2010).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Petoud, S. et al. Brilliant Sm, Eu, Tb, and Dy chiral lanthanide complexes with strong circularly polarized luminescence. J. Am. Chem. Soc. 129, 77–83 (2007). Examples of characteristic luminescence from Tb, Eu, Dy and Sm complexes, including application of two chiral enantiomeric octadentate ligand systems for CPL.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. Ayers, K. M., Schley, N. D. & Ung, G. Circularly polarized luminescence from enantiopure C2-symmetrical tetrakis(2-pyridylmethyl)-1,2-diaminocyclohexane lanthanide complexes. Inorg. Chem. 59, 7657–7665 (2020).

    Article  CAS  PubMed  Google Scholar 

  41. Maupin, C. L., Parker, D., Williams, J. A. G. & Riehl, J. P. Circularly polarized luminescence from chiral octadentate complexes of Yb(iii) in the near-infrared. J. Am. Chem. Soc. 120, 10563–10564 (1998).

    Article  CAS  Google Scholar 

  42. Maupin, C. L. et al. The measurement of circular polarization in the near-IR luminescence from chiral complexes of Yb(iii) and Nd(iii). J. Phys. Chem. A 104, 6709–6717 (2000).

    Article  CAS  Google Scholar 

  43. Doistau, B., Jiménez, J.-R. & Piguet, C. Beyond chiral organic (p-block) chromophores for circularly polarized luminescence: the success of d-block and f-block chiral complexes. Front. Chem. 8, 555 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  44. Peijzel, P. S., Meijerink, A., Wegh, R. T., Reid, M. F. & Burdick, G. W. A complete 4fn energy level diagram for all trivalent lanthanide ions. J. Solid State Chem. 178, 448–453 (2005).

    Article  CAS  Google Scholar 

  45. Kakkar, T., Thomas, N., Kumi-Barimah, E., Jose, G. & Saha, S. Photoluminescence intensity ratio of Eu-conjugated lactates — a simple optical imaging technique for biomarker analysis for critical diseases. J. Biophotonics 11, e201700199 (2018).

    Article  PubMed  CAS  Google Scholar 

  46. Starck, M., Pal, R. & Parker, D. Structural control of cell permeability with highly emissive europium(iii) complexes permits different microscopy applications. Chem. Eur. J. 22, 570–580 (2016).

    Article  CAS  PubMed  Google Scholar 

  47. Dai, L. et al. Synthesis of water-soluble chiral DOTA lanthanide complexes with predominantly twisted square antiprism isomers and circularly polarized luminescence. Inorg. Chem. 58, 12506–12510 (2019).

    Article  CAS  PubMed  Google Scholar 

  48. Mackenzie, L. E. et al. The theoretical molecular weight of NaYF4:RE upconversion nanoparticles. Sci. Rep. 8, 1106 (2018).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  49. Nampi, P. P. et al. Selective cellular imaging with lanthanide based upconversion nanoparticles. J. Biophotonics 12, e201800256 (2018).

    Article  CAS  Google Scholar 

  50. Sugimoto, M. et al. Circularly polarized luminescence from inorganic materials: encapsulating guest lanthanide oxides in chiral silica hosts. Chem. Eur. J. 24, 6519–6524 (2018).

    Article  CAS  PubMed  Google Scholar 

  51. Kumar, J., Marydasan, B., Nakashima, T., Kawai, T. & Yuasa, J. Chiral supramolecular polymerization leading to eye differentiable circular polarization in luminescence. Chem. Commun. 52, 9885–9888 (2016). Describes how the aggregation of monomeric Cs{Eu[(+)-hfbc]4} into helicates boosts CPL emission and affords a glum increase from +1.38 to +1.45.

    Article  CAS  Google Scholar 

  52. Cerdán, L. et al. Circularly polarized laser emission in optically active organic dye solutions. Phys. Chem. Chem. Phys. 19, 22088–22093 (2017).

    Article  PubMed  PubMed Central  Google Scholar 

  53. Jiménez, J. et al. Chiral organic dyes endowed with circularly polarized laser emission. J. Phys. Chem. C 121, 5287–5292 (2017).

    Article  CAS  Google Scholar 

  54. Wu, Y. et al. Rational design of circularly polarized luminescent AIEgens: promoting dissymmetry factor and emission efficiency synchronously. ACS Mater. 2, 505–510 (2020).

    CAS  Google Scholar 

  55. Wan, L. et al. Inverting the handedness of circularly polarized luminescence from light-emitting polymers using film thickness. ACS Nano 13, 8099–8105 (2019).

    Article  CAS  PubMed  Google Scholar 

  56. Raman, C. V. & Bhagavantam, S. Experimental proof of the spin of the photon. Nature 129, 22–23 (1932).

    Article  CAS  Google Scholar 

  57. Beth, R. A. Mechanical detection and measurement of the angular momentum of light. Phys. Rev. 50, 115–125 (1936).

    Article  Google Scholar 

  58. Foss, J. G. Photonic angular momentum and selection rules for rotational transitions. J. Chem. Educ. 47, 778–779 (1970).

    Article  CAS  Google Scholar 

  59. Andrews, D. L. Chirality in fluorescence and energy transfer. Methods Appl. Fluoresc. 7, 032001 (2019).

    Article  CAS  PubMed  Google Scholar 

  60. Torigoe, E. Representing circular polarization with a box of cereal. Phys. Teach. 50, 188–188 (2012).

    Article  Google Scholar 

  61. Shah, A. & Ghalsasi, P. Use of interference colours to distinguish between fast and slow axes of a quarter wave plate. Eur. J. Phys. 40, 065301 (2019).

    Article  Google Scholar 

  62. Schmitzer, H., Tierney, D. & Toepker, T. Real 3-D: how does it work? Phys. Teach. 47, 456–459 (2009).

    Article  Google Scholar 

  63. Chiou, T.-H. et al. Circular polarization vision in a stomatopod crustacean. Curr. Biol. 18, 429–434 (2008).

    Article  CAS  PubMed  Google Scholar 

  64. Roberts, N. W., Chiou, T. H., Marshall, N. J. & Cronin, T. W. A biological quarter-wave retarder with excellent achromaticity in the visible wavelength region. Nat. Photonics 3, 641–644 (2009).

    Article  CAS  Google Scholar 

  65. Brady, P. & Cummings, M. Differential response to circularly polarized light by the jewel scarab beetle Chrysina gloriosa. Am. Nat. 175, 614–620 (2010).

    Article  PubMed  Google Scholar 

  66. Warrant, E. J. Polarisation vision: beetles see circularly polarised light. Curr. Biol. 20, R610–R612 (2010).

    Article  CAS  PubMed  Google Scholar 

  67. Shurcliff, W. A. Haidinger’s brushes and circularly polarized light. J. Opt. Soc. Am. 45, 399 (1955).

    Article  Google Scholar 

  68. Temple, S. E. et al. Perceiving polarization with the naked eye: characterization of human polarization sensitivity. Proc. R. Soc. B Biol. Sci. 282, 20150338 (2015).

    Article  Google Scholar 

  69. Kew, W., Goodall, I., Clarke, D. & Uhrín, D. Chemical diversity and complexity of scotch whisky as revealed by high-resolution mass spectrometry. J. Am. Soc. Mass Spectrom. 28, 200–213 (2017).

    Article  CAS  PubMed  Google Scholar 

  70. Chen, Y. et al. Hollow/rattle-type mesoporous nanostructures by a structural difference-based selective etching strategy. ACS Nano 4, 529–539 (2010).

    Article  CAS  PubMed  Google Scholar 

  71. Meier, W. Polymer nanocapsules. Chem. Soc. Rev. 29, 295–303 (2000).

    Article  CAS  Google Scholar 

  72. Mackenzie, L. E., Pålsson, L.-O., Parker, D., Beeby, A. & Pal, R. Rapid time-resolved circular polarization luminescence (CPL) emission spectroscopy. Nat. Commun. 11, 1676 (2020). Reports the first next-generation rapid SS-CPL spectrometer and demonstrates time-gated CPL measurement in as little as 10 ms.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  73. Bruce, J. I., Parker, D., Lopinski, S. & Peacock, R. D. Survey of factors determining the circularly polarised luminescence of macrocyclic lanthanide complexes in solution. Chirality 14, 562–567 (2002).

    Article  CAS  PubMed  Google Scholar 

  74. Arrico, A. L., Di Bari, L. & Zinna, F. Quantifying the overall efficiency of circularly polarized emitters. Chem. Eur. J. https://doi.org/10.1002/chem.202002791 (2020). Reports CPB values for more than 180 compounds.

    Article  PubMed  Google Scholar 

  75. Sánchez-Carnerero, E. M. et al. Circularly polarized luminescence from simple organic molecules. Chem. Eur. J. 21, 13488–13500 (2015). An excellent review of CPL spectroscopy, including the operation and calibration of legacy SM-CPL spectrometers.

    Article  PubMed  CAS  Google Scholar 

  76. Brittain, H. G. & Richardson, F. S. Circularly polarized emission studies on the chiral nuclear magnetic resonance lanthanide shift reagent tris(3-trifluoroacetyl-d-camphorato)europium(iii). J. Am. Chem. Soc. 98, 5858–5863 (1976). An excellent example of the legacy SM-PEM-CPL spectrometer, establishing the use of [Eu(facam)3] as a CPL reference standard.

    Article  CAS  Google Scholar 

  77. Zhou, Y., Li, H., Zhu, T., Gao, T. & Yan, P. A highly luminescent chiral tetrahedral Eu4L4 (L′)4 cage: chirality induction, chirality memory, and circularly polarized luminescence. J. Am. Chem. Soc. 141, 19634–19643 (2019).

    Article  CAS  PubMed  Google Scholar 

  78. Lunkley, J. L., Shirotani, D., Yamanari, K., Kaizaki, S. & Muller, G. Extraordinary circularly polarized luminescence activity exhibited by cesium tetrakis(3-heptafluoro-butylryl-(+)-camphorato) Eu(iii) complexes in EtOH and CHCl3 solutions. J. Am. Chem. Soc. 130, 13814–13815 (2008).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  79. Lunkley, J. L., Shirotani, D., Yamanari, K., Kaizaki, S. & Muller, G. Chiroptical spectra of a series of tetrakis((+)-3-heptafluorobutylyrylcamphorato)lanthanide(iii) with an encapsulated alkali metal ion: circularly polarized luminescence and absolute chiral structures for the Eu(iii) and Sm(iii) complexes. Inorg. Chem. 50, 12724–12732 (2011). Describes a Cs{Eu[(+)-hfbc]4} complex salt with extraordinarily high CPL (glum = +1.38).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  80. Kitagawa, Y. et al. Chiral lanthanide lumino-glass for a circularly polarized light security device. Commun. Chem. 3, 119 (2020). Demonstrated enantioselective CPL imaging (glum = ±1.2) with a Euiii complex on a glass substrate.

    Article  CAS  Google Scholar 

  81. Frawley, A. T., Pal, R. & Parker, D. Very bright, enantiopure europium(iii) complexes allow time-gated chiral contrast imaging. Chem. Commun. 52, 13349–13352 (2016).

    Article  CAS  Google Scholar 

  82. Metcalf, D. H. et al. Excited-state chiral discrimination observed by time-resolved circularly polarized luminescence measurements. J. Am. Chem. Soc. 111, 3082–3083 (1989).

    Article  CAS  Google Scholar 

  83. Metcalf, D. H., Demas, J. N., Richardson, F. S. & Snyder, S. W. Chiral discrimination in electronic energy-transfer processes between dissymmetric metal complexes in solution. Time-resolved chiroptical luminescence measurements of enantioselective excited-state quenching kinetics. J. Am. Chem. Soc. 112, 5681–5695 (1990).

    Article  CAS  Google Scholar 

  84. Schauerte, J. A., Steel, D. G. & Gafni, A. Time-resolved circularly polarized protein phosphorescence. Proc. Natl Acad. Sci. USA 89, 10154–10158 (1992).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  85. Schauerte, J. A., Schlyer, B. D., Steel, D. G. & Gafni, A. Nanosecond time-resolved circular polarization of fluorescence: study of NADH bound to horse liver alcohol dehydrogenase. Proc. Natl Acad. Sci. USA 92, 569–573 (1995).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  86. Meskers, S. C. J. & Dekkers, H. P. J. M. Enantioselective quenching of luminescence: molecular recognition of chiral lanthanide complexes by biomolecules in solution. J. Phys. Chem. A 105, 4589–4599 (2001).

    Article  CAS  Google Scholar 

  87. Blok, P., Schakel, P. & Dekkers, H. Time-resolved and continuous-wave circular polarisation of luminescence spectroscopy using a commercial spectrofluorimeter. Meas. Sci. Technol. 126, 126–130 (1990).

    Article  Google Scholar 

  88. Glover-Fischer, D. P. et al. Excited-state enantiomer interconversion kinetics probed by time-resolved chiroptical luminescence spectroscopy. The solvent and temperature dependence of Λ-Eu(dpa)33− Δ-Eu(dpa)33− enantiomer interconversion rates in solution. Inorg. Chem. 37, 3026–3033 (1998).

    Article  CAS  Google Scholar 

  89. Beeby, A., Pal, R. & Pålsson, L.-O. Light detecting apparatus for simultaneously detecting left-and right-handed circularly polarised light. Worldwide Patent WO2016174395A1 (2016).

  90. Gendron, F. et al. Luminescence, chiroptical, magnetic and ab-initio crystal-field characterizations of an enantiopure helicoidal Yb(iii) complex: the van Vleck rennaissance. Preprint at ChemRxiv https://doi.org/10.26434/chemrxiv.12473375.v1 (2020).

    Article  Google Scholar 

  91. Frawley, A. T., Linford, H. V., Starck, M., Pal, R. & Parker, D. Enantioselective cellular localisation of europium(iii) coordination complexes. Chem. Sci. 9, 1042–1049 (2018).

    Article  CAS  PubMed  Google Scholar 

  92. Tsumatori, H., Nakashima, T. & Kawai, T. Observation of chiral aggregate growth of perylene derivative in opaque solution by circularly polarized luminescence. Org. Lett. 12, 2362–2365 (2010).

    Article  CAS  PubMed  Google Scholar 

  93. Imai, Y., Nakano, Y., Kawai, T. & Yuasa, J. A smart sensing method for object identification using circularly polarized luminescence from coordination-driven self-assembly. Angew. Chem. Int. Ed. 57, 8973–8978 (2018).

    Article  CAS  Google Scholar 

  94. Tsumatori, H., Harada, T., Yuasa, J., Hasegawa, Y. & Kawai, T. Circularly polarized light from chiral lanthanide(iii) complexes in single crystals. Appl. Phys. Express 4, 17–20 (2011).

    Article  CAS  Google Scholar 

  95. Kumar, J. et al. Circularly polarized luminescence in supramolecular assemblies of chiral bichromophoric perylene bisimides. Chem. Eur. J. 19, 14090–14097 (2013).

    Article  CAS  PubMed  Google Scholar 

  96. Katayama, K., Hirata, S. & Vacha, M. Circularly polarized luminescence from individual microstructures of conjugated polymer aggregates with solvent-induced chirality. Phys. Chem. Chem. Phys. 16, 17983–17987 (2014).

    Article  CAS  PubMed  Google Scholar 

  97. Koike, H., Nozaki, K. & Iwamura, M. Microscopic imaging of chiral amino acids in agar gel through circularly polarized luminescence of Euiii complex. Chem. Asian J. 15, 85–90 (2020).

    Article  CAS  PubMed  Google Scholar 

  98. Mason, S. F., Peackock, R. D. & Stewart, B. Ligand-polarization contributions to the intensity of hypersensitive trivalent lanthanide transitions. Mol. Phys. 30, 1829–1841 (1975).

    Article  CAS  Google Scholar 

  99. Mason, S. F. The ligand polarization model for transition probabilities in the electronic spectra of metal complexes. J. Mol. Struct. 60, 363–366 (1980).

    Article  CAS  Google Scholar 

  100. Reid, M. F. & Richardson, F. S. Electric dipole intensity parameters for lanthanide 4f → 4f transitions. J. Chem. Phys. 79, 5735–5742 (1983).

    Article  CAS  Google Scholar 

  101. Bonsall, S. D., Houcheime, M., Straus, D. A. & Muller, G. Optical isomers of N,N′-bis(1-phenylethyl)-2,6-pyridinedicarboxamide coordinated to europium(iii) ions as reliable circularly polarized luminescence calibration standards. Chem. Commun. 35, 3676–3678 (2007).

    Article  CAS  Google Scholar 

  102. Hua, K. T. et al. Structural and photophysical properties of visible- and near-IR-emitting tris lanthanide(iii) complexes formed with the enantiomers of N,N′-bis(1-phenylethyl)-2,6-pyridinedicarboxamide. Inorg. Chem. 51, 647–660 (2012).

    Article  CAS  PubMed  Google Scholar 

  103. Starck, M., Mackenzie, L., Batsanov, A. S., Parker, D. & Pal, R. Excitation modulation of Eu:BPEPC based complexes as low-energy reference standards for circularly polarised luminescence (CPL). Chem. Commun. 55, 14115–14118 (2019). A suggested new CPL calibration standard to be used with 365-nm UV LED-based excitation.

    Article  CAS  Google Scholar 

  104. Zinna, F., Giovanella, U. & Di Bari, L. Highly circularly polarized electroluminescence from a chiral europium complex. Adv. Mater. 27, 1791–1795 (2015).

    Article  CAS  PubMed  Google Scholar 

  105. Górecki, M., Carpita, L., Arrico, L., Zinna, F. & Di Bari, L. Chiroptical methods in a wide wavelength range for obtaining Ln3+ complexes with circularly polarized luminescence of practical interest. Dalton Trans. 47, 7166–7177 (2018).

    Article  PubMed  Google Scholar 

  106. Butler, S. J. et al. Utility of tris(4-bromopyridyl) europium complexes as versatile intermediates in the divergent synthesis of emissive chiral probes. Dalton Trans. 43, 5721–5730 (2014).

    Article  CAS  PubMed  Google Scholar 

  107. Zhou, Y. et al. Point chirality controlled diastereoselective self-assembly and circularly polarized luminescence in quadruple-stranded europium(iii) helicates. Inorg. Chem. 59, 12850–12857 (2020). Reports tetrahedral Euiii complexes with extraordinarily high CPB values of >1,000 and >3,000 M−1 cm−1.

    Article  CAS  PubMed  Google Scholar 

  108. Zinna, F. et al. Circularly polarized luminescence under near-UV excitation and structural elucidation of a Eu complex. Chem. Commun. 51, 11903–11906 (2015).

    Article  CAS  Google Scholar 

  109. Harada, T. et al. Circularly polarized luminescence from chiral Eu(iii) complex with high emission quantum yield. J. Alloys Compd. 488, 599–602 (2009).

    Article  CAS  Google Scholar 

  110. Harada, T. et al. Nona-coordinated chiral Eu(iii) complexes with stereoselective ligand–ligand noncovalent interactions for enhanced circularly polarized luminescence. Inorg. Chem. 51, 6476–6485 (2012).

    Article  CAS  PubMed  Google Scholar 

  111. Bozoklu, G. et al. Metal-controlled diastereoselective self-assembly and circularly polarized luminescence of a chiral heptanuclear europium wheel. J. Am. Chem. Soc. 134, 8372–8375 (2012).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  112. Arrico, L., De Rosa, C., Di Bari, L., Melchior, A. & Piccinelli, F. Effect of the counterion on circularly polarized luminescence of europium(iii) and samarium(iii) complexes. Inorg. Chem. 59, 5050–5062 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  113. Seitz, M., Moore, E. G., Ingram, A. J., Muller, G. & Raymond, K. N. Enantiopure, octadentate ligands as sensitizers for europium and terbium circularly polarized luminescence in aqueous solution. J. Am. Chem. Soc. 129, 15468–15470 (2007).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  114. Wada, S. et al. The relationship between magneto-optical properties and molecular chirality. NPG Asia Mater. 8, e251 (2016).

    Article  CAS  Google Scholar 

  115. Lama, M. et al. Lanthanide class of a trinuclear enantiopure helical architecture containing chiral ligands: synthesis, structure, and properties. Chem. Eur. J. 13, 7358–7373 (2007).

    Article  CAS  PubMed  Google Scholar 

  116. Leonzio, M. et al. Strongly circularly polarized emission from water-soluble Eu(iii)- and Tb(iii)-based complexes: a structural and spectroscopic study. Inorg. Chem. 56, 4413–4422 (2017).

    Article  CAS  PubMed  Google Scholar 

  117. Seitz, M. et al. Circularly polarized luminescence in enantiopure europium and terbium complexes with modular, all-oxygen donor ligands. Inorg. Chem. 48, 8469–8479 (2009).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  118. Dickins, R. S. et al. Synthesis, time-resolved luminescence, NMR spectroscopy, circular dichroism and circularly polarised luminescence studies of enantiopure macrocyclic lanthanide tetraamide complexes. Chem. Eur. J. 5, 1095–1105 (1999).

    Article  CAS  Google Scholar 

  119. Schnable, D. et al. Synthesis of enantiopure lanthanide complexes supported by hexadentate N,N′-bis(methylbipyridyl)bipyrrolidine and their circularly polarized luminescence. Inorg. Chem. 59, 8498–8504 (2020).

    Article  CAS  PubMed  Google Scholar 

  120. Samuel, A. P. S., Lunkley, J. L., Muller, G. & Raymond, K. N. Strong circularly polarized luminescence from highly emissive terbium complexes in aqueous solution. Eur. J. Inorg. Chem. 21, 3343–3347 (2010).

    Article  CAS  Google Scholar 

  121. Leonard, J. P. et al. Self-assembly of chiral luminescent lanthanide coordination bundles. J. Am. Chem. Soc. 129, 10986–10987 (2007).

    Article  CAS  PubMed  Google Scholar 

  122. Cotter, D., Dodder, S., Klimkowski, V. J. & Hopkins, T. A. Circularly polarized luminescence of Sm (iii) and Eu (iii) complexes with chiral ligand (R/S)-BINAPO. Chirality 31, 301–311 (2019).

    Article  CAS  PubMed  Google Scholar 

  123. Zinna, F., Arrico, L. & Di Bari, L. Near-infrared circularly polarized luminescence from chiral Yb(iii)-diketonates. Chem. Commun. 55, 6607–6609 (2019).

    Article  CAS  Google Scholar 

  124. Beeby, A. et al. Porphyrin sensitization of circularly polarised near-IR lanthanide luminescence: enhanced emission with nucleic acid binding. Chem. Commun. 1, 1183–1184 (2000).

    Article  Google Scholar 

  125. Dee, C. et al. Strong circularly polarized luminescence of an octahedral chromium(iii) complex. Chem. Commun. 55, 13078–13081 (2019).

    Article  CAS  Google Scholar 

  126. Jiménez, J.-R. et al. Chiral molecular ruby [Cr(dqp)2]3+ with long-lived circularly polarized luminescence. J. Am. Chem. Soc. 141, 13244–13252 (2019).

    Article  PubMed  CAS  Google Scholar 

  127. Law, G. L. et al. Circularly polarized luminescence of curium: a new characterization of the 5f actinide complexes. J. Am. Chem. Soc. 134, 15545–15549 (2012).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  128. Liang, J., Guo, P., Qin, X. & Gao, X. Hierarchically chiral lattice self-assembly induced circularly polarized luminescence. ACS Nano 14, 3190–3198 (2020).

    Article  CAS  PubMed  Google Scholar 

  129. OuYang, J. & Crassous, J. Chiral multifunctional molecules based on organometallic helicenes: recent advances. Coord. Chem. Rev. 376, 533–547 (2018).

    Article  CAS  Google Scholar 

  130. Tanaka, H., Inoue, Y. & Mori, T. Circularly polarized luminescence and circular dichroisms in small organic molecules: correlation between excitation and emission dissymmetry factors. ChemPhotoChem 2, 386–402 (2018).

    Article  CAS  Google Scholar 

  131. Kubo, H., Hirose, T. & Matsuda, K. Control over the emission properties of [5]helicenes based on the symmetry and energy levels of their molecular orbitals. Org. Lett. 19, 1776–1779 (2017).

    Article  CAS  PubMed  Google Scholar 

  132. Longhi, G., Castiglioni, E., Abbate, S., Lebon, F. & Lightner, D. A. Experimental and calculated CPL spectra and related spectroscopic data of camphor and other simple chiral bicyclic ketones. Chirality2 25, 589–599 (2013).

    Article  CAS  Google Scholar 

  133. Shiraki, T. et al. Creation of circularly polarized luminescence from an achiral polyfluorene derivative through complexation with helix-forming polysaccharides: Importance of the meta-linkage chain for helix formation. Chem. Asian J. 9, 218–222 (2014).

    Article  CAS  PubMed  Google Scholar 

  134. Watanabe, K., Suda, K. & Akagi, K. Hierarchically self-assembled helical aromatic conjugated polymers. J. Mater. Chem. C 1, 2797–2805 (2013).

    Article  CAS  Google Scholar 

  135. Yang, Y., Da Costa, R. C., Smilgies, D. M., Campbell, A. J. & Fuchter, M. J. Induction of circularly polarized electroluminescence from an achiral light-emitting polymer via a chiral small-molecule dopant. Adv. Mater. 25, 2624–2628 (2013).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  136. Zou, C. et al. Bacterial cellulose: a versatile chiral host for circularly polarized luminescence. Molecules 24, 1008 (2019).

    Article  CAS  PubMed Central  Google Scholar 

  137. Morisaki, Y., Inoshita, K. & Chujo, Y. Planar-chiral through-space conjugated oligomers: synthesis and characterization of chiroptical properties. Chem. Eur. J. 20, 8386–8390 (2014).

    Article  CAS  PubMed  Google Scholar 

  138. Jin, X. et al. Optically active upconverting nanoparticles with induced circularly polarized luminescence and enantioselectively triggered photopolymerization. ACS Nano 13, 2804–2811 (2019).

    Article  CAS  PubMed  Google Scholar 

  139. Clarke, R. et al. Circularly polarised luminescence from helically chiral “confused” N,N,O,C-boron-chelated dipyrromethenes (BODIPYs). ChemPhotoChem 1, 513–517 (2017).

    Article  CAS  Google Scholar 

  140. Sánchez-Carnerero, E. M. et al. Circularly polarized luminescence by visible-light absorption in a chiral O-BODIPY dye: unprecedented design of CPL organic molecules from achiral chromophores. J. Am. Chem. Soc. 136, 3346–3349 (2014).

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  141. Jiménez, J. et al. Modulating ICT emission: a new strategy to manipulate the CPL sign in chiral emitters. Chem. Commun. 55, 1631–1634 (2019).

    Article  Google Scholar 

  142. Li, M. et al. Chiral nanoparticles with full-color and white CPL properties based on optically stable helical aromatic imide enantiomers. ACS Appl. Mater. Interfaces 10, 8225–8230 (2018).

    Article  CAS  PubMed  Google Scholar 

  143. Huo, S., Duan, P., Jiao, T., Peng, Q. & Liu, M. Self-assembled luminescent quantum dots to generate full-color and white circularly polarized light. Angew. Chem. Int. Ed. 56, 12174–12178 (2017).

    Article  CAS  Google Scholar 

  144. Tohgha, U. et al. Ligand induced circular dichroism and circularly polarized luminescence in CdSe quantum dots. ACS Nano 7, 11094–11102 (2013).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  145. Gussakovsky, E. Circularly polarized luminescence (CPL) of proteins and protein complexes. Rev. Fluoresc. 2008, 425–459 (2010).

    Article  CAS  Google Scholar 

  146. Cruz, C. M. et al. Enantiopure distorted ribbon-shaped nanographene combining two-photon absorption-based upconversion and circularly polarized luminescence. Chem. Sci. 9, 3917–3924 (2018).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  147. Chen, J.-F. et al. Planar chiral organoboranes with thermoresponsive emission and circularly polarized luminescence: integration of pillar[5]arenes with boron chemistry. Angew. Chem. Int. Ed. 59, 11267–11272 (2020).

    Article  CAS  Google Scholar 

  148. Pal, R. & Beeby, A. Simple and versatile modifications allowing time gated spectral acquisition, imaging and lifetime profiling on conventional wide-field microscopes. Methods Appl. Fluoresc. 2, 037001 (2014).

    Article  PubMed  CAS  Google Scholar 

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Acknowledgements

L.E.M. and R.P. acknowledge financial support from the Royal Society URF\R\191002, BBSRC BB/S017615/1, EPSRC EP/P025013/1 and a BBSRC Discovery Fellowship BB/T009268/1.

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L.E.M. conducted the review and meta-analysis, wrote the manuscript and designed figures. R.P. edited the manuscript, designed figures and conceived the overall direction of the manuscript.

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Correspondence to Robert Pal.

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MacKenzie, L.E., Pal, R. Circularly polarized lanthanide luminescence for advanced security inks. Nat Rev Chem 5, 109–124 (2021). https://doi.org/10.1038/s41570-020-00235-4

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