TY - JOUR
T1 - New Two-Photon Absorbing BODIPY-Based Fluorescent Probe
T2 - Linear Photophysics, Stimulated Emission, and Ultrafast Spectroscopy
AU - Sui, Binglin
AU - Bondar, Mykhailo V.
AU - Anderson, Dane
AU - Rivera-Jacquez, Hector J.
AU - Masunov, Artëm E.
AU - Belfield, Kevin D.
N1 - Funding Information:
This work was supported in part by the National Science Foundation (CBET-1517273, CHE-0840431, and CHE- 0832622) and the FP7? Marie Curie Actions: ITN Nano2Fun GA #607721. M.V.B. wishes to acknowledge the National Academy of Sciences of Ukraine (grants 1.4.1.B/153 and VC/157). The computational part of this work was performed using the computational resources at The Stokes Advanced Research Computing Center, University of Central Florida (UCF), and the National Energy Research Scientific Computing Center (NERSC). A.E.M. acknowledges support by the Russian Science Foundation, contract no. 14-43-00052.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/7/7
Y1 - 2016/7/7
N2 - The synthesis and comprehensive linear spectroscopic and nonlinear optical properties of a new BODIPY-based fluorene-containing derivative 4,4-difluoro-8-(4-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}phenyl)-1,3,5,7-tetramethyl-2,6-di[(9,9-di{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-9H-fluoren-2-yl)ethynyl]-4-bora-3a,4a-diaza-s-indacene (1) are reported. The steady-state absorption, emission, and excitation anisotropy spectra along with fluorescence lifetimes of 1 were analyzed in organic solvents of different polarity. The degenerate two-photon absorption (2PA) spectrum of 1 was obtained over a broad spectral range by the open aperture Z-scan method using 1 kHz femtosecond excitation, and the 2PA cross section had a maximum value of ∼400 GM. The one-photon stimulated emission depletion spectrum of 1 was determined by a fluorescence quenching method with values of stimulated emission cross sections close to the corresponding ones of the ground state linear absorption. The nature of ultrafast relaxation processes in 1 was analyzed by a transient absorption femtosecond pump-probe technique, and the characteristic times of intramolecular relaxations between the excited electronic states (<150 fs) and solvation dynamics (4-6 ps) were determined. Efficient superluminescence emission of 1 was observed in solution under one- and two-photon femtosecond pumping. Detailed analysis of the singlet excitations in 1 was performed by a time-dependent density functional theory (TD-DFT) method. Three one-photon and two two-photon absorbing states were predicted in the wavelength range investigated. A reactive handle was included in the meso-position of the BODIPY chromophore to facilitate future bioconjugation or functionalization for bioimaging applications.
AB - The synthesis and comprehensive linear spectroscopic and nonlinear optical properties of a new BODIPY-based fluorene-containing derivative 4,4-difluoro-8-(4-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}phenyl)-1,3,5,7-tetramethyl-2,6-di[(9,9-di{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-9H-fluoren-2-yl)ethynyl]-4-bora-3a,4a-diaza-s-indacene (1) are reported. The steady-state absorption, emission, and excitation anisotropy spectra along with fluorescence lifetimes of 1 were analyzed in organic solvents of different polarity. The degenerate two-photon absorption (2PA) spectrum of 1 was obtained over a broad spectral range by the open aperture Z-scan method using 1 kHz femtosecond excitation, and the 2PA cross section had a maximum value of ∼400 GM. The one-photon stimulated emission depletion spectrum of 1 was determined by a fluorescence quenching method with values of stimulated emission cross sections close to the corresponding ones of the ground state linear absorption. The nature of ultrafast relaxation processes in 1 was analyzed by a transient absorption femtosecond pump-probe technique, and the characteristic times of intramolecular relaxations between the excited electronic states (<150 fs) and solvation dynamics (4-6 ps) were determined. Efficient superluminescence emission of 1 was observed in solution under one- and two-photon femtosecond pumping. Detailed analysis of the singlet excitations in 1 was performed by a time-dependent density functional theory (TD-DFT) method. Three one-photon and two two-photon absorbing states were predicted in the wavelength range investigated. A reactive handle was included in the meso-position of the BODIPY chromophore to facilitate future bioconjugation or functionalization for bioimaging applications.
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U2 - 10.1021/acs.jpcc.6b04426
DO - 10.1021/acs.jpcc.6b04426
M3 - Article
AN - SCOPUS:84978160988
SN - 1932-7447
VL - 120
SP - 14317
EP - 14329
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 26
ER -