Unsymmetrical Relaxation Paths of the Excited States in Cyanine Dyes Detected by Time-Resolved Fluorescence: Polymethinic and Polyenic Forms

Petro Lutsyk, Yuri P. Piryatinski, Oleksiy Kachkovsky, Anatoli B. Verbitsky, Oleksiy Rozhin

Research output: Contribution to journalArticle

Abstract

Novel applications of organic dyes and vast opportunities for their molecular tailoring keep focus of scientific community on the issues of symmetry breaking in the systems having different location of uncompensated charge, which has tremendous impact on photoluminescent properties of the dyes. In this paper, we provide distinctive experimental evidences of three relaxation paths (one symmetrical and two unsymmetrical) of excited states by analysis of lifetime and spectra of time-resolved fluorescence at low temperature with strong support of quantum-chemical modeling. Importantly, the studied cyanine dye (astraphloxin) in aqueous solution has two different unsymmetrical relaxation paths of excites states in the polymethinic and donor-acceptor polyenic forms, where the last form strongly diminishes in less polar media. The experimental and computational results provide essential fundamental knowledge of molecular electronic relaxations substantially affected by matrix rigidity and polarity for design and photonic applications of elongated π-electronic systems.
Original languageEnglish
JournalJournal of Physical Chemistry: Part A
VolumeIn press
Early online date9 Oct 2017
DOIs
Publication statusE-pub ahead of print - 9 Oct 2017

Fingerprint

Excited states
Coloring Agents
dyes
Fluorescence
fluorescence
excitation
Molecular electronics
molecular electronics
rigidity
Rigidity
Photonics
broken symmetry
polarity
photonics
aqueous solutions
life (durability)
matrices
electronics
Temperature

Bibliographical note

Copyright: 2017, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry: Part A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b08680.

Funding:EU FP ‘Horizon-2020’ Marie Skłodowska-Curie Individual Fellowship (FOC4SIP, #654733).

Cite this

@article{045f7231b39f4cf7a1cbb8b20e1e89a1,
title = "Unsymmetrical Relaxation Paths of the Excited States in Cyanine Dyes Detected by Time-Resolved Fluorescence: Polymethinic and Polyenic Forms",
abstract = "Novel applications of organic dyes and vast opportunities for their molecular tailoring keep focus of scientific community on the issues of symmetry breaking in the systems having different location of uncompensated charge, which has tremendous impact on photoluminescent properties of the dyes. In this paper, we provide distinctive experimental evidences of three relaxation paths (one symmetrical and two unsymmetrical) of excited states by analysis of lifetime and spectra of time-resolved fluorescence at low temperature with strong support of quantum-chemical modeling. Importantly, the studied cyanine dye (astraphloxin) in aqueous solution has two different unsymmetrical relaxation paths of excites states in the polymethinic and donor-acceptor polyenic forms, where the last form strongly diminishes in less polar media. The experimental and computational results provide essential fundamental knowledge of molecular electronic relaxations substantially affected by matrix rigidity and polarity for design and photonic applications of elongated π-electronic systems.",
author = "Petro Lutsyk and Piryatinski, {Yuri P.} and Oleksiy Kachkovsky and Verbitsky, {Anatoli B.} and Oleksiy Rozhin",
note = "Copyright: 2017, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry: Part A, copyright {\circledC} American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b08680. Funding:EU FP ‘Horizon-2020’ Marie Skłodowska-Curie Individual Fellowship (FOC4SIP, #654733).",
year = "2017",
month = "10",
day = "9",
doi = "10.1021/acs.jpca.7b08680",
language = "English",
volume = "In press",
journal = "Journal of Physical Chemistry: Part A",
issn = "1089-5639",
publisher = "American Chemical Society",

}

Unsymmetrical Relaxation Paths of the Excited States in Cyanine Dyes Detected by Time-Resolved Fluorescence : Polymethinic and Polyenic Forms. / Lutsyk, Petro; Piryatinski, Yuri P.; Kachkovsky, Oleksiy; Verbitsky, Anatoli B.; Rozhin, Oleksiy.

In: Journal of Physical Chemistry: Part A, Vol. In press, 09.10.2017.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Unsymmetrical Relaxation Paths of the Excited States in Cyanine Dyes Detected by Time-Resolved Fluorescence

T2 - Polymethinic and Polyenic Forms

AU - Lutsyk, Petro

AU - Piryatinski, Yuri P.

AU - Kachkovsky, Oleksiy

AU - Verbitsky, Anatoli B.

AU - Rozhin, Oleksiy

N1 - Copyright: 2017, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry: Part A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b08680. Funding:EU FP ‘Horizon-2020’ Marie Skłodowska-Curie Individual Fellowship (FOC4SIP, #654733).

PY - 2017/10/9

Y1 - 2017/10/9

N2 - Novel applications of organic dyes and vast opportunities for their molecular tailoring keep focus of scientific community on the issues of symmetry breaking in the systems having different location of uncompensated charge, which has tremendous impact on photoluminescent properties of the dyes. In this paper, we provide distinctive experimental evidences of three relaxation paths (one symmetrical and two unsymmetrical) of excited states by analysis of lifetime and spectra of time-resolved fluorescence at low temperature with strong support of quantum-chemical modeling. Importantly, the studied cyanine dye (astraphloxin) in aqueous solution has two different unsymmetrical relaxation paths of excites states in the polymethinic and donor-acceptor polyenic forms, where the last form strongly diminishes in less polar media. The experimental and computational results provide essential fundamental knowledge of molecular electronic relaxations substantially affected by matrix rigidity and polarity for design and photonic applications of elongated π-electronic systems.

AB - Novel applications of organic dyes and vast opportunities for their molecular tailoring keep focus of scientific community on the issues of symmetry breaking in the systems having different location of uncompensated charge, which has tremendous impact on photoluminescent properties of the dyes. In this paper, we provide distinctive experimental evidences of three relaxation paths (one symmetrical and two unsymmetrical) of excited states by analysis of lifetime and spectra of time-resolved fluorescence at low temperature with strong support of quantum-chemical modeling. Importantly, the studied cyanine dye (astraphloxin) in aqueous solution has two different unsymmetrical relaxation paths of excites states in the polymethinic and donor-acceptor polyenic forms, where the last form strongly diminishes in less polar media. The experimental and computational results provide essential fundamental knowledge of molecular electronic relaxations substantially affected by matrix rigidity and polarity for design and photonic applications of elongated π-electronic systems.

U2 - 10.1021/acs.jpca.7b08680

DO - 10.1021/acs.jpca.7b08680

M3 - Article

VL - In press

JO - Journal of Physical Chemistry: Part A

JF - Journal of Physical Chemistry: Part A

SN - 1089-5639

ER -