danДоклады Национальной академии наук БеларусиDoklady of the National Academy of Sciences of Belarus1561-83232524-2431The Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8323-2021-65-3-281-289dan-973Research ArticleФИЗИКАPHYSICSСпектральная динамика нестационарного поглощения гибридных ассоциатов квантовых точек CdS и красителя метиленового голубогоTransient absorption spectral dynamics of hybrid associates of CdS quantum dots and methylene blue dyeТихомировС. А.TikhomirovS. A.

Тихомиров Сергей Александрович – член-корреспондент, д-р физ.-мат. наук, гл. науч. сотрудник

пр. Независимости, 68-2, 220072, Минск, Республика Беларусь

Tikhomirov Sergey A. – Corresponding Member, D. Sc. (Physics and Mathematics), Chief researcher

68-2, Nezavisimosti Ave., 220072, Minsk, Republic of Belarus

s.tik@dragon.bas-net.byИнститут физики им. Б. И. Степанова Национальной академии наук БеларусиB. I. Stepanov Institute of Physics of the National Academy of Sciences of Belarus202115072021653281289Copyright © Тихомиров С.А., 20212021Тихомиров С.А.Tikhomirov S.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://doklady.belnauka.by/jour/article/view/973

Методами фемтосекундной абсорбционной спектроскопии исследована спектрально-временная динамика нестационарного поглощения гибридных ассоциатов коллоидных квантовых точек CdS, пассивированных тиогликолевой кислотой (CdS/TGA), и молекул катионного красителя метиленового голубого (MB+), а также составляющих их компонентов. Установлено, что одним из основных каналов релаксации энергии экситонного возбуждения в гибридных ассоциатах на основе квантовых точек CdS/TGA и метиленового голубого является быстрый перенос энергии к восстановленным формам MBOH• (МB•) в составе ассоциатов, формируемым еще на стадии синтеза образцов, составляющий конкуренцию резонансному переносу энергии от центров излучательной рекомбинации в квантовых точках к MB+.

The transient absorption spectra dynamics for hybrid associates of colloidal CdS quantum dots, passivated by thioglycolic acid (CdS/TGA QDs), and methylene blue cationic dye molecules (MB+) were studied by femtosecond spectroscopy. It was established that one of the main channels of relaxation of the CdS/TGA QDs excitation energy in hybrid associates based on CdS/TGA QDs and MB+ is a fast energy transfer to the reduced forms of MB+ (MBOH•, MB•) that are formed still at the synthesis stage of samples. This channel strongly competes with the resonant energy transfer from the centers of radiative recombination in quantum dots to MB+. Therefore, for hybrid associates based on QDs/TGA and methylene blue, there is no any noticeable signal of the transient absorption corresponding to the triplet state of MB+ dye, which is then known to be actively involved in charge transfer.

гибридные ассоциатынестационарные спектры поглощенияфемтосекундная спектроскопияперенос энергииhybrid associatesnonstationary absorption spectrafemtosecond spectroscopyenergy transferReferencesChou, K. Forster resonance energy transfer between quantum dot donors and quantum dot acceptors / K. Chou, A. Dennis // Sensors. – 2015. – Vol. 15, N 6. – P. 13288–13325. https://doi.org/10.3390/s150613288Chou K., Dennis A. Forster resonance energy transfer between quantum dot donors and quantum dot acceptors. Sensors, 2015, vol. 15, no. 6, pp. 13288–13325. https://doi.org/10.3390/s150613288Electronic processes within quantum dot-molecule complexes / R. D. Harris [et al.] // Chem. Rev. – 2016. – Vol. 116, N 21. – P. 12865–12919. https://doi.org/10.1021/acs.chemrev.6b00102Harris R. D., Homan S. B., Kodaimati M., He C., Nepomnyashchii A. B., Swenson N. K., Lian S., Calzada R., Weiss E. A. Electronic processes within quantum dot-molecule complexes. Chemical Reviews, 2016, vol. 116, no. 21, pp. 12865–12919. https://doi.org/10.1021/acs.chemrev.6b00102Luminescence properties of hybrid associates of colloidal CdS quantum dots with J-aggregates of thiatrimethine cyanine dye / M. S. Smirnov [et al.] // J. Lumin. – 2016. – Vol. 176. – P. 77–85. https://doi.org/10.1016/j.jlumin.2016.03.015Smirnov M. S., Ovchinnikov O. V., Dedikova A. O., Shapiro B. I., Vitukhnovsky A. G., Shatskikh T. S. Luminescence properties of hybrid associates of colloidal CdS quantum dots with J-aggregates of thiatrimethine cyanine dye. Journal of Luminescence, 2016, vol. 176, pp. 77–85. https://doi.org/10.1016/j.jlumin.2016.03.015CdTe quantum dot/dye hybrid system as photosensitizer for photodynamic therapy / A. Rakovich [et al.] // Nanoscale Research Letters. – 2010. – Vol. 5, N 4. – P. 753–760. https://doi.org/10.1007/s11671-010-9553-xRakovich A., Savateeva D., Rakovich T., Donegan J. F., Rakovich Y. P., Kelly V., Lesnyak V., Eychmüller A. CdTe quantum dot/dye hybrid system as photosensitizer for photodynamic therapy. Nanoscale Research Letters, 2010, vol. 5, no. 4, pp. 753–760. https://doi.org/10.1007/s11671-010-9553-xPhotoexcitation dynamics in hybrid associates of Ag2S quantum dots with methylene blue / M. S. Smirnov [et al.] // Journal of Luminescence. – 2021. – Vol. 232. – Art. 117794. https://doi.org/10.1016/j.jlumin.2020.117794Smirnov M. S., Buganov O. V., Tikhomirov S. A., Ovchinnikov O. V. Photoexcitation dynamics in hybrid associates of Ag2S quantum dots with methylene blue. Journal of Luminescence, 2021, vol. 232, art. 117794. https://doi.org/10.1016/j.jlumin.2020.117794Multiple Exciton Dissociation in CdSe Quantum Dots by Ultrafast Electron Transfer to Adsorbed Methylene Blue / J. Huang [et al.] // J. Am. Chem. Soc. – 2010. – Vol. 132, N 13. – P. 4858–4864. https://doi.org/10.1021/ja100106zHuang J., Huang Z., Yang Y., Zhu H., Lian T. Multiple Exciton Dissociation in CdSe Quantum Dots by Ultrafast Electron Transfer to Adsorbed Methylene Blue. Journal of the American Chemical Society, 2010, vol. 132, no. 13, pp. 4858–4864. https://doi.org/10.1021/ja100106zA thin CdSe shell boosts the electron transfer from CdTe quantum dots to methylene blue / L. Dworak [et al.] // Nanoscale. – 2018. – Vol. 10, N 4. – P. 2162–2169. https://doi.org/10.1039/c7nr08287hDworak L., Roth S., Scheffer M. P., Frangakis A. S., Wachtveitl J. A thin CdSe shell boosts the electron transfer from CdTe quantum dots to methylene blue. Nanoscale, 2018, vol. 10, no. 4, pp. 2162–2169. https://doi.org/10.1039/c7nr08287hYang, Y. Ultrafast Charge Separation and Recombination Dynamics in Lead Sulfide Quantum Dot-Methylene Blue Complexes Probed by Electron and Hole Intraband Transitions / Y. Yang, W. Rodríguez-Cordoba, T. Lian // J. Am. Chem. Soc. – 2011. – Vol. 133, N 24. – P. 9246–9249. https://doi.org/10.1021/ja2033348Yang Y., Rodríguez-Cordoba W., Lian T. Ultrafast Charge Separation and Recombination Dynamics in Lead Sulfide Quantum Dot-Methylene Blue Complexes Probed by Electron and Hole Intraband Transitions. Journal of the American Chemical Society, 2011, vol. 133, no. 24, pp. 9246–9249. https://doi.org/10.1021/ja2033348Yang, Ye. Multiple exciton dissociation and hot electron extraction by ultrafast interfacial electron transfer from PbS QDs / Ye Yang, Tianquan Lian // Coordination Chemistry Reviews. – 2014. – Vol. 263–264. – P. 229–238. https://doi.org/10.1016/j.ccr.2013.11.013Yang Y., Lian T. Multiple exciton dissociation and hot electron extraction by ultrafast interfacial electron transfer from PbS QDs. Coordination Chemistry Reviews, 2014, vol. 263–264, pp. 229–238. https://doi.org/10.1016/j.ccr.2013.11.013Influence of Negatively Charged Interfaces on the Ground and Excited State Properties of Methylene Blue / D. Severino [et al.] // Photochemistry and Photobiology. – 2007. – Vol. 77, N 5. – P. 459–468. https://doi.org/10.1562/0031-8655(2003)0770459ioncio2.0.co2Severino D., Junqueira H. C., Gugliotti M., Gabrielli D. S., Baptista M. S. Influence of Negatively Charged Interfaces on the Ground and Excited State Properties of Methylene Blue. Photochemistry and Photobiology, 2007, vol. 77, no. 5, pp. 459–468. https://doi.org/10.1562/0031-8655(2003)0770459ioncio2.0.co2Gak, V. Yu. Triplet-excited dye molecules (eosine and methylene blue) quenching by H2O2 in aqueous solutions / V. Yu. Gak, V. A. Nadtochenko, J. Kiwi // Journal of Photochemistry and Photobiology A: Chemistry. – 1998. – Vol. 116. – P. 57–62. https://doi.org/10.1016/s1010-6030(98)00230-5Gak V., Nadtochenko V., Kiwi J. Triplet-excited dye molecules (eosine and methylene blue) quenching by H2O2 in aqueous solutions. Journal of Photochemistry and Photobiology A: Chemistry, 1998, vol. 116, no. 1, pp. 57–62. https://doi.org/10.1016/s1010-6030(98)00230-5Decay of electronic excitations in colloidal thioglycolic acid (TGA)-capped CdS/ZnS quantum dots / M. S. Smirnov [et al.] // J. Nanopart. Res. – 2017. – Vol. 19, N 11. – Art. 376. https://doi.org/10.1007/s11051-017-4067-4Smirnov M. S., Buganov O. V., Tikhomirov S. A., Ovchinnikov O. V., Shabunya-Klyachkovskaya E. V., Grevtseva I. G., Kondratenko T. S. Decay of electronic excitations in colloidal thioglycolic acid (TGA)-capped CdS/ZnS quantum dots. Journal of Nanoparticle Research, 2017, vol. 19, no. 11, art. 376. https://doi.org/10.1007/s11051-017-4067-4Charge transfer process determines ultrafast excited state deactivation of thioflavin T in low-viscosity solvents / V. I. Stsiapura [et al.] // J. Phys. Chem. A. – 2010. – Vol. 114, N 32. – P. 8345−8350. https://doi.org/10.1021/jp105186zStsiapura V. I., Maskevich A. A., Tikhomirov S. A., Buganov O. V. Charge transfer process determines ultrafast excited state deactivation of thioflavin T in low-viscosity solvents. Journal of Physical Chemistry A, 2010, vol. 114, no. 32, pp. 8345−8350. https://doi.org/10.1021/jp105186zDimeric and other forms of methylene blue: Absorption and fluorescence of the pure monomer1 / G. N. Lewis [et al.] // J. Am. Chem. Soc. – 1943. – Vol. 65, N 6. – P. 1150–1154. http://doi.org/10.1021/ja01246a037Lewis G. N., Goldschmid O., Magel T. T., Bigeleisen J. Dimeric and other forms of methylene blue: Absorption and fluorescence of the pure monomer1. Journal of American Chemical Society, 1943, vol. 65, no. 6, pp. 1150–1154. http://doi.org/10.1021/ja01246a037Nekrasov, A. D. Effect of multiply charged paramagnetic metal cations on J-aggregation of thiacyanine dyes / A. D. Nekrasov, B. I. Shapiro // High Energy Chemistry. – 2011. – Vol. 45, N 2. – P. 133–139. https://doi.org/10.1134/s001814391102010xNekrasov A. D., Shapiro B. I. Effect of multiply charged paramagnetic metal cations on J-aggregation of thiacyanine dyes. High Energy Chemistry, 2011, vol. 45, no. 2, pp. 133–139. https://doi.org/10.1134/s001814391102010xSolvent effect on the electronic spectra of azine dyes under alkaline condition / S. Basu [et al.] // J. Phys. Chem. A. – 2007. – Vol. 111, N 4. – P. 578–583. http://doi.org/10.1021/jp065740uBasu S., Panigrahi S., Praharaj S., Ghosh S. K., Pande S., Jana S., Pal A., Pal T. Solvent effect on the electronic spectra of azine dyes under alkaline condition. Journal of Physical Chemistry A, 2007, vol. 111, no. 4, pp. 578–583. http://doi.org/10.1021/jp065740u

The authors declare that there are no conflicts of interest present.