Efficient Two-Photon Absorbing Acceptor-π-Acceptor Polymethine Dyes

Abstract

We present an experimental and theoretical investigation of the linear and nonlinear optical properties of a series of acceptor-pi-acceptor symmetrical anionic polymethine dyes with diethylamino-coumarin-dioxaborine terminal groups and different conjugation lengths. Two-photon absorption (2PA) cross sections (delta(2PA)) are enhanced with an increase of pi-conjugation length in the investigated series of dyes. 2PA spectra for all dyes consist of two well-separated bands. The first band, located within the telecommunications window, occurs upon two-photon excitation into the vibrational levels of the main S(0) --> S(1) transition, reaching a large delta(2PA) = 2200 GM (1 GM = 1 x 10(-50) cm(4) s/photon) at 1600 nm for the longest conjugated dye. The position of the second, and strongest, 2PA band for all anionic molecules corresponds to the second-excited final state, which is confirmed by quantum-chemical calculations and excitation anisotropy measurements. Large delta(2PA) values up to 17,000 GM at 1100 nm are explained by the combination of the large ground- and excited-state transition dipole moments. The three shortest dyes show good photochemical stability and surprisingly large fluorescence quantum yields of approximately 0.90, approximately 0.66, and approximately 0.18 at the red to near-IR region of approximately 640, approximately 730, and approximately 840 nm, respectively. The excited-state absorption spectra for all samples are also studied and exhibit intense bands throughout the visible wavelength region with peak cross section close to 5 x 10(-16) cm(2) with a corresponding red shift with increasing conjugation lengths.

Molecular design of near infrared polymethine dyes: A review

“…As an illustration, the absorption spectra of dyes 4 derivatives of aminocoumarine synthesized by A.O. Gerasev et al [83][84][85][86][87] are presented in Figure 1b.…”

“…Gerasev et al [155][156][157] for the anionic polymethine dyes 4. Combined quantum-chemical and spectral studies of the dyes 4 [85][86][87] have shown that two lowest electron transitions are split transitions, involving two low positioned acceptor levels, in contrast to the cationic cyanine dyes where two lowest transitions are connected with two split donor levels.…”

The crystal structure of 2,2-difluoro-4-(trifluoromethyl)-2,5-dihydro-[1,3,2]dioxaborinino[5,4-c]chromen-3-ium-2-uide, C11H6BF5O3

“…Difluoroboron compounds have wide range applications in sensors, optoelectronic devices, probes, and catalysis in the past few years [3][4][5][6]. Herein, we report the crystal structure of difluoroboron 3-(2,2,2-trifluoroacetyl)chroman-4-one.…”

Red Emitting Coumarins: Insights of Photophysical Properties with DFT Methods

“…The positions 5 and 7 when substituted with a donor moiety such as -OH, −NEt 2 , −NH 2 and -OCH 3 and the positions 3 and 4 substituted with acceptors like -CN, −COOEt and benzazolyl group, the coumarin fluorophore experiences a red shifted absorption and hence red shifted emission. Increasing the rigidity of the donor [46] and acceptor [47] groups also adds to the red shift of the coumarin molecules. The substitution at 4-position by -CN group (an acceptor) induces a red shift in the emission of coumarins [44].…”