Two-Photon Absorption Spectrum of a Single Crystal Cyanine-like Dye.
The two-photon absorption (2PA) spectrum of an organic single crystal is reported. The crystal is grown by self-nucleation of a subsaturated hot solution of acetonitrile, and is composed of an asymmetrical donor-π-acceptor cyanine-like dye molecule. To our knowledge, this is the first report of the 2PA spectrum of single crystals made from a cyanine-like dye. The linear and nonlinear properties of the single crystalline material are investigated and compared with the molecular properties of a toluene solution of its monomeric form. The maximum polarization-dependent 2PA coefficient of the single crystal is 52 ± 9 cm/GW, which is more than twice as large as that for the inorganic semiconductor CdTe with a similar absorption edge. The optical properties, linear and nonlinear, are strongly dependent upon incident polarization due to anisotropic molecular packing. X-ray diffraction analysis shows π-stacking dimers formation in the crystal, similar to H-aggregates. Quantum chemical calculations demonstrate that this dimerization leads to the splitting of the energy bands and the appearance of new red-shifted 2PA bands when compared to the solution of monomers. This trend is opposite to the blue shift in the linear absorption spectra upon H-aggregation.
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.
Honghua
H
Hu
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.
Dmitry A
DA
Fishman
‡Institute of Organic Chemistry, National Academy of Sciences, Murmanskaya 5, Kiev, 03094, Ukraine.
Andrey O
AO
Gerasov
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.|§Institute of Physics, National Academy of Sciences, Prospect Nauki 46, Kiev, 03028, Ukraine.
Olga V
OV
Przhonska
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.
Scott
S
Webster
∥Center for Advanced Solar Photophysics, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States.
Lazaro A
LA
Padilha
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.
Davorin
D
Peceli
‡Institute of Organic Chemistry, National Academy of Sciences, Murmanskaya 5, Kiev, 03094, Ukraine.
Mykola
M
Shandura
‡Institute of Organic Chemistry, National Academy of Sciences, Murmanskaya 5, Kiev, 03094, Ukraine.
Yuriy P
YP
Kovtun
‡Institute of Organic Chemistry, National Academy of Sciences, Murmanskaya 5, Kiev, 03094, Ukraine.
Alexey D
AD
Kachkovski
⊥NanoScience Technology Center, University of Central Florida, Orlando, Florida 32826, United States.|#Department of Chemistry, University of Central Florida, Orlando, Florida 32816, United States.|▽Department of Physics, University of Central Florida, Orlando, Florida 32816, United States.|○Florida Solar Energy Center, University of Central Florida, Orlando, Florida 32816, United States.
Iffat H
IH
Nayyar
⊥NanoScience Technology Center, University of Central Florida, Orlando, Florida 32826, United States.|#Department of Chemistry, University of Central Florida, Orlando, Florida 32816, United States.|▽Department of Physics, University of Central Florida, Orlando, Florida 32816, United States.|○Florida Solar Energy Center, University of Central Florida, Orlando, Florida 32816, United States.
Artëm E
AE
Masunov
◆Department of Biology and Chemistry, New Mexico Highlands University, Las Vegas, New Mexico 87701, United States.
Paul
P
Tongwa
◆Department of Biology and Chemistry, New Mexico Highlands University, Las Vegas, New Mexico 87701, United States.
Tatiana V
TV
Timofeeva
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.|▽Department of Physics, University of Central Florida, Orlando, Florida 32816, United States.
David J
DJ
Hagan
†CREOL, The College of Optics and Photonics, University of Central Florida, Orlando, Florida 32816, United States.|▽Department of Physics, University of Central Florida, Orlando, Florida 32816, United States.
Eric W
EW
Van Stryland
cyanine-like dye; dimer formation; organic crystal; two-photon absorption