TY - JOUR
T1 - Electronic Nature of Nonlinear Optical Properties of a Symmetrical Two-Photon Absorbing Fluorene Derivative
T2 - Experimental Study and Theoretical Modeling
AU - Kurhuzenkau, Siarhei A.
AU - Colon Gomez, Maria Yezabel
AU - Belfield, Kevin D.
AU - Shaydyuk, Yevgeniy O.
AU - Hagan, David J.
AU - Van Stryland, Eric W.
AU - Sissa, Cristina
AU - Bondar, Mykhailo V.
AU - Painelli, Anna
N1 - Funding Information:
This research was funded by the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/ under REA grant agreement no. 607721 (Nano2Fun). M.V.B. acknowledges the support from the National Academy of Sciences of Ukraine (grants B-180 and VC/188). K.D.B. acknowledges the support from the National Science Foundation (CBET-1517273), while M.Y.C.G. acknowledges the support from the Arnold and Mabel Beckman Foundation and the University of Central Florida 2009 Beckman Scholars program. The authors thank Sheng Yao (University of Central Florida) for assistance in thesynthesis of 1. E.W.V.S. and D.J.H. thank the Army Research Laboratory (W911NF-15-2-0090) and the National Science Foundation grant DMR-1609895 for the support.
Funding Information:
This research was funded by the People Programme (Marie Curie Actions) of the European Union’s Seventh Framework Programme FP7/2007-2013/ under REA grant agreement no. 607721 (Nano2Fun). M.V.B. acknowledges the support from the National Academy of Sciences of Ukraine (grants B-180 and VC/188). K.D.B. acknowledges the support from the National Science Foundation (CBET-1517273), while M.Y.C.G. acknowledges the support from the Arnold and Mabel Beckman Foundation and the University of Central Florida 2009 Beckman Scholars program. The authors thank Sheng Yao (University of Central Florida) for assistance in the synthesis of 1. E.W.V.S. and D.J.H. thank the Army Research Laboratory (W911NF-15-2-0090) and the National Science Foundation grant DMR-1609895 for the support.
PY - 2018/3/15
Y1 - 2018/3/15
N2 - A comprehensive experimental and theoretical study of linear photophysical properties, such as excited-state relaxation, two-photon absorption, and stimulated emission spectra of the symmetrical fluorene derivative 2,2′-((1E,1′E)-(9,9-diethyl-9H-fluorene-2,7-diyl)bis(ethene-2,1-diyl))bis(1-methyl-1H-pyrrole) (1), is presented. The steady-state absorption, fluorescence, excitation, and excitation anisotropy spectra of 1 in organic solvents of different polarities are investigated experimentally and modeled. The fluorescence solvatochromism of 1 suggests the occurrence of symmetry breaking in the first excited state. The nature of fast relaxation processes in the excited state of 1, with the characteristic times of several picoseconds, is investigated by transient absorption femtosecond pump-probe spectroscopy. The spectral properties of 1 are satisfactorily described by an essential-state model that, accounting for electron-vibration coupling and for polar solvation, addresses spectroscopic features not only in terms of band position and intensities but also in terms of band shapes. Specifically, we present the first calculation of frequency-resolved two-photon-excited fluorescence anisotropy spectra. Our results demonstrate that electron-vibration coupling and polar solvation quite naturally explain the puzzling experimental observation of large deviations of the anisotropies from the values expected on the basis of the relative orientation of the molecular transition dipole moments.
AB - A comprehensive experimental and theoretical study of linear photophysical properties, such as excited-state relaxation, two-photon absorption, and stimulated emission spectra of the symmetrical fluorene derivative 2,2′-((1E,1′E)-(9,9-diethyl-9H-fluorene-2,7-diyl)bis(ethene-2,1-diyl))bis(1-methyl-1H-pyrrole) (1), is presented. The steady-state absorption, fluorescence, excitation, and excitation anisotropy spectra of 1 in organic solvents of different polarities are investigated experimentally and modeled. The fluorescence solvatochromism of 1 suggests the occurrence of symmetry breaking in the first excited state. The nature of fast relaxation processes in the excited state of 1, with the characteristic times of several picoseconds, is investigated by transient absorption femtosecond pump-probe spectroscopy. The spectral properties of 1 are satisfactorily described by an essential-state model that, accounting for electron-vibration coupling and for polar solvation, addresses spectroscopic features not only in terms of band position and intensities but also in terms of band shapes. Specifically, we present the first calculation of frequency-resolved two-photon-excited fluorescence anisotropy spectra. Our results demonstrate that electron-vibration coupling and polar solvation quite naturally explain the puzzling experimental observation of large deviations of the anisotropies from the values expected on the basis of the relative orientation of the molecular transition dipole moments.
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U2 - 10.1021/acs.jpcc.7b12397
DO - 10.1021/acs.jpcc.7b12397
M3 - Article
AN - SCOPUS:85044161875
SN - 1932-7447
VL - 122
SP - 5664
EP - 5672
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 10
ER -