3,5-Bis(acetaldehyde) substituted BODIPY.

Two versions of a facile and efficient synthetic approach to 3,5-bis(acetaldehyde) substituted BODIPY have been developed and this compound has been used to obtain, in high yields, a variety of 3,5-divinyl BODIPY derivatives (vinylacetates, enamines, vinyl chlorides, and some multiple-functionalized products). As shown, vinyl substituents have an additive effect on the position of the BODIPY absorption maximum. The dyes synthesized are quite stable and exhibit intense absorption and fluorescence with wavelengths longer than 600 nm.

Efficient two-photon absorbing acceptor-pi-acceptor polymethine dyes.

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.