Linear Optical and Third-Order Nonlinear Optical Properties of Some Fluorenyl- and Triarylamine-Containing Tetracyanobutadiene Derivatives.
The synthesis and characterization of four new tetracyanobutadiene (TCBD) derivatives (1-3 and 2') incorporating 2- or 2,7-fluorenyl and diphenylamino moieties are reported. The electroactivity of 1-3 and 2' was studied by cyclic voltammetry (CV), while the linear optical and (third-order) nonlinear optical (NLO) properties were investigated by electronic spectroscopy and Z-scan studies, respectively. All experimental investigations were rationalized by DFT computations, providing an insight into the electronic structure of these derivatives and on their application potential. We show that these derivatives are nonluminescent in solution at ambient temperatures, but become fluorescent in solvent glasses. This finding constitutes an unprecedented observation for TCBD derivatives. Also, we show by Z-scan studies that these derivatives behave as two-photon absorbers in the near-IR range (800-1050 nm). These third-order NLO properties are discussed and compared with those of their alkynyl precursors (4-6), which have been investigated by two-photon excited fluorescence (TPEF).
Faculty of Chemistry, Wroclaw University of Science and Technology, 50-370, Wroclaw, Polen.
Ziemowit
Z
Pokladek
Institut des Sciences Chimiques de Rennes, CNRS (UMR 6226), Université de Rennes 1, Campus de Beaulieu, 35042, Rennes Cedex, France.|Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.
Nicolas
N
Ripoche
Ecole Nationale Supérieure de Chimie de Rennes, CNRS (UMR 6226), Institut des Sciences Chimiques de Rennes, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.
Marie
M
Betou
Ecole Nationale Supérieure de Chimie de Rennes, CNRS (UMR 6226), Institut des Sciences Chimiques de Rennes, 11 allée de Beaulieu, CS 50837, 35708, Rennes Cedex 7, France.
Yann
Y
Trolez
Institut des Sciences Chimiques de Rennes, CNRS (UMR 6226), Université de Rennes 1, Campus de Beaulieu, 35042, Rennes Cedex, France.
Olivier
O
Mongin
Faculty of Chemistry, Wroclaw University of Science and Technology, 50-370, Wroclaw, Polen.
Joanna
J
Olesiak-Banska
Faculty of Chemistry, Wroclaw University of Science and Technology, 50-370, Wroclaw, Polen. katarzyna.matczyszyn@pwr.edu.pl.
Katarzyna
K
Matczyszyn
Faculty of Chemistry, Wroclaw University of Science and Technology, 50-370, Wroclaw, Polen.
Marek
M
Samoc
Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.
Mark G
http://orcid.org/0000-0002-4433-6783
MG
Humphrey
ISM, CNRS (UMR 5255), Université Bordeaux, 33400, Talence, France.
Mireille
M
Blanchard-Desce
Institut des Sciences Chimiques de Rennes, CNRS (UMR 6226), Université de Rennes 1, Campus de Beaulieu, 35042, Rennes Cedex, France. frederic.paul@univ-rennes1.fr.
Frédéric
F
Paul
alkynes; arynes; fluorescence; luminescence; tetracyanobutadiene; two-photon absorption