N‐BODIPYs (diaminoboron dipyrromethenes) are unveiled as a new family of BODIPY dyes with huge technological potential. Synthetic access to these systems has been gained through a judicious design focused on stabilizing the involved diaminoboron chelate. Once stabilized, the obtained N‐BODIPYs retain the effective photophysical behavior exhibited by other boron‐substituted BODIPYs, such as O‐BODIPYs. However, key bonding features of nitrogen compared to those of oxygen (enhanced bond valence and different bond directionality) open up new possibilities for functionalizing BODIPYs, allowing an increase in the number of pendant moieties (from two in O‐BODIPYs, up to four in N‐BODIPYs) near the chromophore and, therefore, greater control of the photophysics. As a proof of concept, the following findings are discussed: (1) the low‐cost and straightforward synthesis of a selected series of N‐BODIPYs; (2) their outstanding photophysical properties compared to those of related effective dyes (excellent emission signatures, including fluorescence in the solid state; notable lasing capacities in the liquid phase and when doped into polymers; improved laser performance compared to the parent F‐BODIPYs); (3) the versatility of the diaminoboron moiety in allowing the generation of multifunctionalized BODIPYs, permitting access to both symmetric and asymmetric dyes; (4) the capability of such versatility to finely modulate the dye photophysics towards different photonic applications, from lasing to chemosensing.
Simple organic molecules (SOM) based on bis(haloBODIPY) are shown to enable circularly polarized luminescence (CPL) conforming a new structural design for technologically-valuable CPL-SOMs. The established design comprises, all-in-one, synthetic accessibility, labile helicity, possibility of reversing the handedness of the circularly polarized emission and reactive functional groups, making it unique and attractive as advantageous platform for the development of smart CPL-SOMs.
A series of uncommon bis(BODIPYs), involving a flexible bridge linking the BODIPY α-positions and key functionalities to efficiently give an electronic push-pull effect, has been synthesized, as well as photophysically and structurally studied. It is demonstrated that the designed push-pull effect efficiently enables intramolecular charge transfer (ICT) processes upon photoexcitation, with the generated low-lying ICT state being the main deactivation channel from the locally excited state and, hence, ruling the fluorescence response. Noticeably, this response is modulated by the solvent polarity, and also by the bridge structure. Regarding this, BINOL- and BINAM-based bridges are found to promote an interesting unprecedented solvent-switchable dual emission from the ICT state with high Stokes shifts, triggering a significant bright red emission in less polar media.
A general and straightforward
method for the synthesis of COO-BODIPYs
from F-BODIPYs and carboxylic acids is established. The method is
based on the use of boron trichloride to activate the involved substitution
of fluorine, which leads to high yields through rapid reactions under
soft conditions. This mild method opens the way to unprecedented laser
dyes with outstanding efficiencies and photostabilities, which are
difficult to obtain by the current methods.
COO-BODIPYs are highlighted as cutting edge scaffolds for the easy access to a new generation of multichromophoric architectures with enhanced (photo)chemical stability, showing either boosted capability for excitation energy transfer,...
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