SYNTHESIS AND ABSORPTION SPECTRA OF INDOTRICARBOCYANINE DYES WITH ELECTRON-DONATING GROUPS IN THE MESO-POSITION OF THE POLYMETHINE CHAIN
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Keywords

cyanine dyes, indoheptamethinecyanines, polymethine chromophore, donor substituents, bridging groups.

How to Cite

Sharanov, I., & Slominskii, Y. (2023). SYNTHESIS AND ABSORPTION SPECTRA OF INDOTRICARBOCYANINE DYES WITH ELECTRON-DONATING GROUPS IN THE MESO-POSITION OF THE POLYMETHINE CHAIN. Ukrainian Chemistry Journal, 89(2), 109-124. https://doi.org/10.33609/2708-129X.89.02.2023.109-124

Abstract

Recently, a large number of studies have been dedicated to chemistry and physical stu­dies of polymethine dyes, especially to the functio­na­lized symmetrical heptamethinecyanines based on the indole derivatives. Due to their unique and versatile spectral properties, which lie in the near infrared region (NIR), meso-substituted indotricarbocyanine dyes are widely used in various physical and biological fields. In the present work, we have developed methods of synthesis of a series of indotricarbocyanine dyes with di- and trimethylene bridging groups in the γ,γ'-positions and donor substituents in the meso-position of the polymethine chromophore and studied their effects on the spectral properties of the dyes. The obtained data indicated that the change of the substituent in the meso-position of the chromophore and the presence of a poly­me­thylene bridging groups allow to vary signi­ficantly the absorption maxima of the synthesized indoheptamethinecyanine dyes without altering the length of the polymethine chain. It was shown that the electron-donating nitrogen-containing substituents lead, according to the Forster-Dewar-Knott rule, to a hypsochromic shifts of the absorption maxima. However, it was found that the methoxy group in the meso-position of the polymethine chromophore in some cases exhibited unexpected "acceptor" properties due to a certain steric hindrance, resulting in a red shift of the absorption band, in contrast to the other donor substituents. Additionally, the effects of the insertion of di- and trimethylene bridging groups to the polymethine chain of the cyanine dyes on their spectral properties were studied.  The synthesized meso-substituted indotricarbocyanines demonstrated significant solvatochromism and spectral properties that lie in the red and near-infrared regions.

https://doi.org/10.33609/2708-129X.89.02.2023.109-124
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References

Gorka A., Nani R., Schnermann M. Cyanine polyene reactivity: scope and biomedical applications. Org. Biomol. Chem. 2015. 13 (28): 7584–7598. doi: 10.1039/c5o600788g.

Zhang D., Zou J., Chen W., Yiu S., Tse M., Luo J., Jen A. Efficient, stable, and scalable push-pull heptamethines for electro-optics. Chem. Mater. 2022. 34 (8): 3683–3693.

doi: 10.1021/acs.chemmater.1c04339.

Bricks J. L., Kachkovskii A. D., Slominskii Y. L., Gerasov A. O., Popov S. V. Molecular design of near infrared polymethine dyes: a review. Dyes Pigm., 2015. 121: 238–255.

doi: 10.1016/j.dyepig.2015.05.016.

Voiciuk V., Redeckas K., Derevyanko N., Kulinich A., Barkauskas M., Vengris M., Sirutkaitis V., Ishchenko A. Study of photophysical properties of a series of poly­methine dyes by femtosecond laser photolysis. Dyes Pigm. 2014. 109: 120–126.

doi: 10.1016/j.dyepig.2014.05.012.

Ishchenko A. A. Photonics and molecular design of dye-doped polymers for modern light-sensitive materials. Pure Appl. Chem. 2008. 80 (7): 1525–1538.

doi: 10.1351/pac200880071525.

Exner R. M., Cortezon-Tamarit F., Pascu S. I. Explorations into the effect of meso-substituents in tricarbocyanine dyes: a path to diverse biomolecular probes and materials. Angew. Chem. Int. Ed. 2021. 60 (12): 6230–6241.

doi: 10.1002/anie.202008075

Shi Ch., Wu J., Pan D. Review on near-infrared heptamethine cyanine dyes as theranostic agents for tumor imaging, targeting, and photodynamic therapy. J Biomed Opt. 2016. 21 (5): 05091-I–05091-II.

doi: 10.1117/1.JBO.21.5.050901.

Qian, G. and Wang Z.Y. Near-Infrared Organic Compounds and Emerging Applications. Chem. Asian J. 2010. 5: 1006–1029.

doi: 10.1002/asia.200900596.

Górecki T., Patonay G., Strekowski L., Chin R., Salazar N. Synthesis of novel near-infrared cyanine dyes for metal ion determination. J. He­terocycl. Chem. 1996. 33 (6): 1871–1876.

doi: 10.1002/jhet.5570330652.

Strekowski L., Lipowska M., Patonay G. Substitution reactions of a nucleofugal group in heptamethine cyanine dyes. Synthesis of an isothiocyanato derivative for labeling of proteins with a near-infrared chromophore. J. Org. Chem. 1992. 57 (17): 4578–4580.

doi: 10.1021/jo00043a009.

Ilchenko A. Y. Fundamentals of the theory of chromaticity of organic dyes. Nauk. dum.,Kyiv. 2012. 6: 119–126.

Slominskii Y. L., Radchenko I. D. Condensation of dimethinehemicyanines with ketones. Chem. heterocycl. 1974. 5: 711–712.

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