Probing of Higher Excited States of Merocyanine Derivatives of Azaazulene and Indandione by Fluorescence Excitation Anisotropy Spectra

Authors

  • A. P. Naumenko Taras Shevchenko National University of Kyiv
  • V. I. Borysuk Taras Shevchenko National University of Kyiv
  • M. S. Iakhnenko Taras Shevchenko National University of Kyiv
  • V. O. Gubanov Taras Shevchenko National University of Kyiv
  • Y. L. Slominskii Institute of Organic Chemistry, Nat. Acad. of Sci. of Ukraine
  • O. D. Kachkovsky V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry, Nat. Acad. of Sci. of Ukraine

DOI:

https://doi.org/10.15407/ujpe65.4.321

Keywords:

polymethine dyes, absorption spectra, fluorescence spectra, anisotropy of fluorescence excitation, quantum-chemical calculations

Abstract

This paper is dedicated to the spectral and quantum-chemical studies of higher excited states of merocyanine derivatives of azaazulene and indandione. A particular attention is paid to the analysis of fluorescence excitation anisotropy spectra of the mentioned compounds. The long-wave shift by ≈ 50 nm of a deep clear minimum in the fluorescence excitation anisotropy spectrum due to an elongation of the polymethine dye chromophore is established. Such shift is close in a value to the bathochromic shift of the first minimum in the anisotropy spectrum of symmetric ionic polymethine dyes, in which this minimum corresponds to the second electronic transition. The parallel spectral study and quantum-chemical calculations allowed us to correctly interpret the fluorescence excitation anisotropy spectra of merocyanines and relate the first clear minimum with the seventh electronic transition. The last resembles the second electronic transition between delocalized molecular orbitals (MO) in polymethine dyes.

References

J.R. Lakowicz. Principles of Fluorescence Spectroscopy (Academic/Plenum, 1999).

https://doi.org/10.1007/978-1-4757-3061-6

R.A. Negres, O.V. Przhonska, D.J. Hagan, E.W. Van Stryland, M.V. Bondar, Yu.L. Slominsky, A.D. Kachkovski. IEEE J. Selected Topics Quantum Electron 7, 849 (2001). https://doi.org/10.1109/2944.979347

R.S. Lepkowicz, O.V. Przhonska, J.M. Hales, D.J. Hagan, E.W. Van Stryland, M.V. Bondar, Yu.L. Slominsky, A.D. Kachkovski. Excited-state absorption dynamics in polymethine dyes detected by polarization-resolved pump-probe measurements. Chem. Phys. 286, 277 (2003). https://doi.org/10.1016/S0301-0104(02)00937-0

O.V. Przhonska, L.A. Padilha, D.J. Hagan, E.W. Van Stryland, K.D. Belfield, M.V. Bondar, Yu.L. Slominsky, A.D. Kachkovski. Two-photon anisotropy: analytical description and molecular modeling for symmetrical and asymmetrical organic dyes. Chem. Phys. 321, 257 (2006). https://doi.org/10.1016/j.chemphys.2005.08.021

O. Przhonska, S. Webster, L. Padilha, H. Hu, A. Kachkovski, D. Hagan, E.V. Stryland. Two-photon absorption in near-IR conjugated molecules: design strategy and structure-property relations. In: Advanced Fluorescence Reporters in Chemistry and Biology I: Fundamentals and Molecular Design, Springer Series in Fluorescence, Vol. 8, (Springer, 2010), pp. 105-147. https://doi.org/10.1007/978-3-642-04702-2_4

A.V. Stanova, A.B. Ryabitsky, V.M. Yashchuk, O.D. Kachkovsky, A.O. Gerasov, Ya.O. Prostota, O.V. Kropachev. Asymmetry in ground and excited states in styryls and methoxystyryls detected by NMR (13 C), absorption, fluorescence and fluorescence excitation spectroscopy. J. Molec. Struct. 988, 102 (2011). https://doi.org/10.1016/j.molstruc.2010.12.038

L.A. Padilha, S. Webster, O.V. Przhonska, H. Hu, D. Peceli, J.L. Rosch et al. Efficient two-photon absorbing acceptor-p-acceptor polymethine dyes. J. Phys. Chem. A 114, 6493 (2010). https://doi.org/10.1021/jp100963e

L.A. Padilha, S. Webster, O.V. Przhonska, H. Hu, D. Peceli, J.L. Rosch et al. Nonlinear absorption in a series of donor-p-acceptor cyanines with different conjugation lengths. J. Mater. Chem. 19, 7503 (2009). https://doi.org/10.1039/b907344b

O.V. Przhonska, H. Hu, S. Webster, J.L. Bricks, A.A. Viniychuk, A.D. Kachkovski, Yu.L. Slominsky. Electronic transitions in a series of 2-azaazulene polymethine dyes with different п-conjugation lengths. Chem. Phys. 411, 17 (2013). https://doi.org/10.1016/j.chemphys.2012.11.017

O.O. Viniychuk, S.M. Levchenko, O.V. Przhonska, O.D. Kachkovsky, Yu.L. Bricks, M.O. Kudinova, Yu.P. Kovtun, Ye.M. Poronik, M.P. Shandura, O.I. Tolmachev. Electronic transitions in polymethine dyes involving local and delocalized levels. J. Molec. Struct. 1060, 30 (2014). https://doi.org/10.1016/j.molstruc.2013.12.038

J.L. Bricks, A.D. Kachkovskii, Yu.L. Slominskii, A.O. Gerasov, S.V. Popov. Molecular design of near infrared polymethine dyes: A review. Dyes and Pigments 121, 238 (2015). https://doi.org/10.1016/j.dyepig.2015.05.016

O. Chernega, S. Levchenko, A. Ryabitskii, A. Gerasov, O. Kachkovskii, Yu. Yagupolskii. Nature of the lowest electron transitions of thia- and quinocyanines with fluorinated polymethine chain. Dyes and Pigments. 123, 176 (2015). https://doi.org/10.1016/j.dyepig.2015.07.037

J.L. Bricks, A.V. Stanova, A.B. Ryabitsky, V.M. Yashchuk, A.D. Kachkovsky. Studies of 2-azaazulenium derivatives - 3: The nature of electron transitions and spectral properties of styryl dyes containing terminal groups of different types. J. Molec. Struct. 1033, 215 (2013). https://doi.org/10.1016/j.molstruc.2012.08.034

M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al. GAUSSIAN 09 Revision B.05 (GAUSSIAN, 2003).

J. Fabian. TDDFT-calculations of Vis/NIR absorbing compounds. Dyes and Pigments 84, 36 (2009). https://doi.org/10.1016/j.dyepig.2009.06.008

S Karaca, N. Elmaci. A computational study on the excited state properties of a cationic cyanine dye: TTBC. Comput. Theor. Chem. 964, 160 (2011). https://doi.org/10.1016/j.comptc.2010.12.016

D. Jacquemin, Ya. Zhao, R. Valero, C. Adamo, I. Ciofini, D.G. Truhlar. Verdict: Time-dependent density functional theory "Not guilty" of large errors for cyanines. J. Chem. Theory Comput. 8, 1255 (2012). https://doi.org/10.1021/ct200721d

Downloads

Published

2020-04-17

How to Cite

Naumenko, A. P., Borysuk, V. I., Iakhnenko, M. S., Gubanov, V. O., Slominskii, Y. L., & Kachkovsky, O. D. (2020). Probing of Higher Excited States of Merocyanine Derivatives of Azaazulene and Indandione by Fluorescence Excitation Anisotropy Spectra. Ukrainian Journal of Physics, 65(4), 321. https://doi.org/10.15407/ujpe65.4.321

Issue

Section

Optics, atoms and molecules

Most read articles by the same author(s)

<< < 1 2