Linear photophysics, ultrafast relaxations and superfluorescence in two-photon absorbing fluorene derivative

Siarhei Kurhuzenkau1,  Sheng Yao2,  Adam Woodward2,  Kevin Belfield3,  Anna Painelli1,  Cristina Sissa1,  Yevgeniy Shaydyuk4,  Mykhailo Bondar4
1Department of Chemistry, University of Parma, Parco Area delle Scienze 17/A, Parma, 43124, Italy, 2Department of Chemistry, University of Central Florida, Orlando, FL 32816-2366, USA, 3College of Science and Liberal Arts, New Jersey Institute of Technology, University Heights, Newark, NJ 07102, USA, 4Institute of Physics NASU, Prospect Nauki, 46, Kiev-28, 03028, Ukraine


Abstract

We present a comprehensive photophysical and photochemical characterization of a newly synthesized donor-acceptor (DA) substituted fluorene, 3,3'-(2-(benzo[d]thiazol-2-yl)-7-(diethylamino)-9H-fluorene-9,9-diyl)dipropanen itrile (1), of interest for nonlinear optical application. The charge-transfer nature of the low-energy transition of 1 was determined based on absorption, fluorescence and excitation anisotropy spectra collected at room temperature in organic solvents of different polarity. As expected for a charge-transfer DA dye with a largely neutral ground state, absorption spectra are marginally solvatochromic while fluorescence spectra show a sizable solvatochromism. Fluorescence lifetime measurements reveal monoexponential decay kinetics in all solvents. The values of the photostability quantum yield of 1 in different solvents were determined by the absorption method. The data showed that 1 has relatively high photostability, which is crucial for its practical application. Degenerate two-photon absorption spectrum of 1 was determined in a broad spectral range using open aperture Z-scan methodology and 1 kHz femtosecond excitation. The nature of ultrafast relaxation processes in the excited electronic states of 1 was investigated by femtosecond transient absorption pump-probe spectroscopic technique and two different types of fast relaxations with the characteristic times of 0.5 - 1.0 ps and 5 - 8 ps were detected. Efficient superfluorescence properties of 1 were observed in liquid medium under transverse pumping by femtosecond laser beam. Obtained results, supported by an extensive theoretical characterization, reveal a high potential of 1 for application in a number of nonlinear optical techniques, including two-photon laser scanning fluorescence microscopy. The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/ under REA grant agreement n°607721.