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Title: Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations

Abstract

Here corroles are emerging as an important class of macrocycles with numerous applications because of their peculiar photophysical and metal chelating properties. meso-Pyrimidinylcorroles are easily deprotonated in certain solvents, which changes their absorption and emission spectra as well as their accessible supramolecular structures. To enable control over the formation of supramolecular structures, the dominant corrole species, i.e., the deprotonated form or one of the two NH-tautomers, needs to be identified. Therefore, we focus in the present article on the determination of the UV–vis spectroscopic properties of the free-base NH-tautomers and the deprotonated form of a new amphiphilic meso-pyrimidinylcorrole that can assemble to supramolecular structures at heterointerfaces as utilized in the Langmuir–Blodgett and liquid–liquid interface precipitation techniques. After quantification of the polarities of the free-base NH-tautomers and the deprotonated form by means of quantum chemically derived electrostatic potential distributions at the corroles’ van der Waals surfaces, the preferential stabilization of (some of) the considered species in solvents of different polarity is identified by means of absorption spectroscopy. For the solutions with complex mixtures of species, we applied fluorescence excitation spectroscopy to estimate the relative weights of the individual corrole species. This technique might also be applied to identify dominating species inmore » molecularly thin films directly on the subphase’ surface of Langmuir–Blodgett troughs. Supported by quantum chemical calculations we were able to differentiate between the spectral signatures of the individual NH-tautomers by means of fluorescence excitation spectroscopy.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [2];  [6]; ORCiD logo [7]; ORCiD logo [8]
  1. Friedrich Schiller Univ. Jena, Jena (Germany); Leibniz Institute of Photonic Technology (IPHT), Jena (Germany)
  2. National Institute for Material Science, Ibaraki (Japan)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  4. Friedrich Schiller Univ. Jena, Jena (Germany); Leibniz Institute of Photonic Technology (IPHT), Jena (Germany); Center for Energy and Environmental Chemistry Jena (CEEC Jena), Jena (Germany)
  5. National Institute for Materials Science, Ibaraki (Japan)
  6. Belarusian State Technological Univ., Minsk (Belarus)
  7. UHasselt - Hasselt Univ., Diepenbeek (Belgium)
  8. Friedrich Schiller Univ. Jena, Jena (Germany); Leibniz Institute of Photonic Technology (IPHT), Jena (Germany); Center for Energy and Environmental Chemistry Jena (CEEC Jena), Jena (Germany); Sciclus GmbH Co., Jena (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1463313
Grant/Contract Number:  
AC02-76SF00515; 03EK3507; JP16H06518
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 45; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Preiß, Julia, Herrmann-Westendorf, Felix, Ngo, Thien H., Martínez, Todd, Dietzek, Benjamin, Hill, Jonathan P., Ariga, Katsuhiko, Kruk, Mikalai M., Maes, Wouter, and Presselt, Martin. Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpca.7b08910.
Preiß, Julia, Herrmann-Westendorf, Felix, Ngo, Thien H., Martínez, Todd, Dietzek, Benjamin, Hill, Jonathan P., Ariga, Katsuhiko, Kruk, Mikalai M., Maes, Wouter, & Presselt, Martin. Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations. United States. https://doi.org/10.1021/acs.jpca.7b08910
Preiß, Julia, Herrmann-Westendorf, Felix, Ngo, Thien H., Martínez, Todd, Dietzek, Benjamin, Hill, Jonathan P., Ariga, Katsuhiko, Kruk, Mikalai M., Maes, Wouter, and Presselt, Martin. Wed . "Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations". United States. https://doi.org/10.1021/acs.jpca.7b08910. https://www.osti.gov/servlets/purl/1463313.
@article{osti_1463313,
title = {Absorption and Fluorescence Features of an Amphiphilic meso-Pyrimidinylcorrole: Experimental Study and Quantum Chemical Calculations},
author = {Preiß, Julia and Herrmann-Westendorf, Felix and Ngo, Thien H. and Martínez, Todd and Dietzek, Benjamin and Hill, Jonathan P. and Ariga, Katsuhiko and Kruk, Mikalai M. and Maes, Wouter and Presselt, Martin},
abstractNote = {Here corroles are emerging as an important class of macrocycles with numerous applications because of their peculiar photophysical and metal chelating properties. meso-Pyrimidinylcorroles are easily deprotonated in certain solvents, which changes their absorption and emission spectra as well as their accessible supramolecular structures. To enable control over the formation of supramolecular structures, the dominant corrole species, i.e., the deprotonated form or one of the two NH-tautomers, needs to be identified. Therefore, we focus in the present article on the determination of the UV–vis spectroscopic properties of the free-base NH-tautomers and the deprotonated form of a new amphiphilic meso-pyrimidinylcorrole that can assemble to supramolecular structures at heterointerfaces as utilized in the Langmuir–Blodgett and liquid–liquid interface precipitation techniques. After quantification of the polarities of the free-base NH-tautomers and the deprotonated form by means of quantum chemically derived electrostatic potential distributions at the corroles’ van der Waals surfaces, the preferential stabilization of (some of) the considered species in solvents of different polarity is identified by means of absorption spectroscopy. For the solutions with complex mixtures of species, we applied fluorescence excitation spectroscopy to estimate the relative weights of the individual corrole species. This technique might also be applied to identify dominating species in molecularly thin films directly on the subphase’ surface of Langmuir–Blodgett troughs. Supported by quantum chemical calculations we were able to differentiate between the spectral signatures of the individual NH-tautomers by means of fluorescence excitation spectroscopy.},
doi = {10.1021/acs.jpca.7b08910},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 45,
volume = 121,
place = {United States},
year = {2017},
month = {10}
}

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