The Synthesis and Spectral Properties of Merocyanine Dyes Based on 9H‑Fluorene-2,7-Dicarbonitrile

Iryna V. Kurdiukova; Volodymyr V. Kurdyukov; Andrii V. Kulinich

doi:10.24959/ophcj.25.350444

Authors

Iryna V. Kurdiukova Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0001-6695-8535
Volodymyr V. Kurdyukov Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-7668-5435
Andrii V. Kulinich Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-0857-6632

DOI:

https://doi.org/10.24959/ophcj.25.350444

Keywords:

merocyanines, fluorene, electronic absorption spectra, solvatochromism, TD-DFT calculations

Abstract

Di-, tetra-, and hexamethine merocyanine dyes bearing donor heterocyclic end groups of different electron-donating abilities and the 9H-fluorene-2,7-dicarbonitrile moiety as the acceptor end group have been synthesized. Their UV/Vis absorption spectra have been studied in solvents of varying polarity, and their electronic nature and vertical transitions have been investigated via (TD)-DFT calculations. The results indicate that the electronic structure of these merocyanines approaches the neutral polyene limit, becoming increasingly polyene-like in low-polarity solvents and upon increasing the polymethine chain length, which indicates the weak electron-acceptor ability of the 9H-fluorene-2,7-dicarbonitrile moiety. Nevertheless, longer vinylogs, especially those containing the 4H-pyran donor end group, exhibit the inverse solvatochromic behavior, which is highly unusual for such weakly dipolar merocyanines. A possible explanation for this effect has been proposed although its rigorous verification would require higher-level quantum-chemical calculations with solvent effects taken into account.

Supporting Agency

The authors received no specific funding for this work.

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References

Mishra, A.; Behera, R. K.; Behera, P. K.; Mishra, B. K.; Behera, G. B. Cyanines during the 1990s: A Review. Chem. Rev. 2000, 100 (6), 1973-2012. https://doi.org/10.1021/cr990402t.
| |
Kulinich, A. V.; Ishchenko, A. A. Merocyanines: Electronic Structure and Spectroscopy in Solutions, Solid State, and Gas Phase. Chem. Rev. 2024, 124 (21), 12086-12144. https://doi.org/10.1021/acs.chemrev.4c00317.
| |
Kurdyukova, I. V.; Ishchenko, A. A. Organic dyes based on fluorene and its derivatives. Russ. Chem. Rev. 2012, 81 (3), 258. https://doi.org/10.1070/RC2012v081n03ABEH004211.
|
Kurdyukova, I. V.; Ishchenko, A. A.; Derevyanko, N. A.; Mysyk, D. D. Synthesis and Spectral Properties of Merocyanine Dyes Derived from Tetranitrofluorene and Heterocycles of Various Electron-donating Ability. Chem. Heterocycl. Comp. 2013, 49 (2), 281-293. https://doi.org/10.1007/s10593-013-1245-x.
|
Kulinich, A. V.; Ishchenko, A. A.; Groth, U. M. Electronic structure and solvatochromism of merocyanines: NMR spectroscopic point of view. Spectrochim. Acta, Part A 2007, 68 (1), 6-14. https://doi.org/10.1016/j.saa.2006.10.043.
| |
Kulinich, A. V.; Derevyanko, N. A.; Ishchenko, A. A. Electronic structure and solvatochromism of merocyanines based on N,N-diethylthiobarbituric acid. J. Photoch. Photobio. A 2007, 188 (2), 207-217. https://doi.org/10.1016/j.jphotochem.2006.12.014.
|
Dähne, S. Der Ideale Polymethinzustand . Chimia 1991, 45 (10), 288. https://doi.org/10.2533/chimia.1991.288.
Reichardt, C.; Welton, T. Solvents and solvent effects in organic chemistry: Fourth edition, Wiley-VCH, Weinheim, 2010. https://doi.org/10.1002/9783527632220.
König, W. Über den Begriff der „Polymethinfarbstoffe”︁ und eine davon ableitbare allgemeine Farbstoff-Formel als Grundlage einer neuen Systematik der Farbenchemie. Journal für Praktische Chemie 1926, 112 (1), 1-36. https://doi.org/10.1002/prac.19261120101.
Reynolds, G. A.; Drexhage, K. H. Stable heptamethine pyrylium dyes that absorb in the infrared. J. Org. Chem. 1977, 42 (5), 885-888. https://doi.org/10.1021/jo00425a027.
|
Pascal, S.; Getmanenko, Y. A.; Zhang, Y.; Davydenko, I.; Ngo, M. H.; Pilet, G.; Redon, S.; Bretonnière, Y.; Maury, O.; Ledoux-Rak, I.; Barlow, S.; Marder, S. R.; Andraud, C. Design of Near-Infrared-Absorbing Unsymmetrical Polymethine Dyes with Large Quadratic Hyperpolarizabilities. Chem. Mater. 2018, 30 (10), 3410-3418. https://doi.org/10.1021/acs.chemmater.8b00960.
|
Renge, I. Refractive index dependence of solvatochromism. J. Photoch. Photobio. A 2018, 353, 433-444. https://doi.org/10.1016/j.jphotochem.2017.11.048.
|
Ishchenko, A. A.; Svidro, V. A.; Derevyanko, N. A. Solvatofluorochromy of cationic cyanine dyes. Dyes Pigments 1989, 10 (2), 85-96. https://doi.org/10.1016/0143-7208(89)85001-6.
|
Catalán, J. Toward a Generalized Treatment of the Solvent Effect Based on Four Empirical Scales: Dipolarity (SdP, a New Scale), Polarizability (SP), Acidity (SA), and Basicity (SB) of the Medium. J. Phys. Chem. B 2009, 113 (17), 5951-5960. https://doi.org/10.1021/jp8095727.
| |
Meyers, F.; Marder, S. R.; Pierce, B. M.; Bredas, J. L. Electric Field Modulated Nonlinear Optical Properties of Donor-Acceptor Polyenes: Sum-Over-States Investigation of the Relationship between Molecular Polarizabilities (.alpha., .beta., and .gamma.) and Bond Length Alternation. J. Am. Chem. Soc. 1994, 116 (23), 10703-10714. https://doi.org/10.1021/ja00102a040.
|
Fabian, J. TDDFT-calculations of Vis/NIR absorbing compounds. Dyes Pigments 2010, 84 (1), 36-53. https://doi.org/10.1016/j.dyepig.2009.06.008.
|
Tomar, R.; Bernasconi, L.; Fazzi, D.; Bredow, T. Theoretical Study on the Optoelectronic Properties of Merocyanine-Dyes. J. Phys. Chem. A 2023, 127 (46), 9661-9671. https://doi.org/10.1021/acs.jpca.3c04226.
| |
Plasser, F. On the Meaning of De-Excitations in Time-Dependent Density Functional Theory Computations. J. Comput. Chem. 2025, 46 (8), e70072. https://doi.org/10.1002/jcc.70072.
| |
Armarego, W. L. F.; Chai, C. Purification of Laboratory Chemicals, 6th ed., Butterworth-Heinemann, Oxford, 2009. https://doi.org/10.1016/C2009-0-26589-5.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A.; Bloino, J.; Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J. V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.; Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson, T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.; Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Throssell, K.; Montgomery Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.; Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Farkas, O.; Foresman, J. B.; Fox, D. J. Gaussian 09, Rev. D.01, Gaussian Inc., Wallingford, CT. (2009).
Becke, A. D. Density‐functional thermochemistry. III. The role of exact exchange. The Journal of Chemical Physics 1993, 98 (7), 5648-5652. https://doi.org/10.1063/1.464913.
|
Spychala, J. A Convenient Way to Methylated 2-Imidazolines. Syntheses of Fluorene and Triazine Cyclic Diamidines. Monatsh Chem 2006, 137 (9), 1203-1210. https://doi.org/10.1007/s00706-006-0516-y.
|
Andreu, R.; Carrasquer, L.; Franco, S.; Garín, J.; Orduna, J.; Martínez de Baroja, N.; Alicante, R.; Villacampa, B.; Allain, M. 4H-Pyran-4-ylidenes: Strong Proaromatic Donors for Organic Nonlinear Optical Chromophores. J. Org. Chem. 2009, 74 (17), 6647-6657. https://doi.org/10.1021/jo901142f.
| |