Near‐IR BODIPY Dyes à la Carte—Programmed Orthogonal Functionalization of Rationally Designed Building Blocks

Abstract

Herein, we report the synthesis of polyfunctional BODIPY building blocks suitable to be subjected to several reaction sequences with complete chemoselectivity, thereby allowing the preparation of complex BODIPY derivatives in a versatile and programmable manner. The reactions included the Liebeskind-Srogl cross-coupling reaction (LSCC), nucleophilic aromatic substitution (SN Ar), Suzuki, Sonogashira, and Stille couplings, and a desulfitative reduction of the MeS group. This novel synthetic protocol is a powerful route to design a library of compounds with tailored photophysical properties for advanced applications. In this context, it is noteworthy that it offers a straightforward and cost-effective strategy to shift the BODIPY emission deep into the near-infrared spectral region while retaining high fluorescence quantum yields as well as highly efficient and stable laser action. These new dyes outperform the lasing behaviour of dyes considered as benchmarks over the red spectral region, overcoming the important drawbacks associated with these commercial laser dyes, namely low absorption at the standard pump wavelengths (355 and 532 nm) and/or poor photostability.

BODIPY Dyes Bearing Multibranched Fluorinated Chains: Synthesis, Structural, and Spectroscopic Studies

“…In addition to the presence of one or more fluorinated residues able to provide an intense, single 19 F NMR signal, two other main guidelines were followed in the design of the fluorinated BODIPYs under study. First, two iodine atoms were placed on the BODIPY core to provide a dual feature: working as replaceable functional groups through orthogonal synthesis with the perspective of preparing more complex structures, and promoting efficient singlet oxygen generation, similarly to previously developed halogenated BODIPYs used as effective phototherapeutic agents . Second, an increased delocalization of the π electrons was pursued by extending conjugation through a condensation reaction of the acid methyl groups in the 3,5‐positions of the preformed BODIPYs with a suitable aromatic aldehyde …”

Towards Efficient and Photostable Red‐Emitting Photonic Materials Based on Symmetric All‐BODIPY‐Triads, ‐Pentads, and ‐Hexads

“…Thus, the extinction coefficient at the red‐edge maximum wavelength reached up to 170 000 m −1 cm −1 for compound 10 , bearing two π‐extended central BODIPYs, whereas this absorption coefficient at the green–yellow maximum wavelength became even higher than 200 000 m −1 cm −1 for dyes 9 and 10 , bearing four pendant peripheral BODIPYs (Figure ). Finally, an absorption band placed at the ultraviolet edge (360 nm in Figures ) was recorded and was attributed to the interaction of the styryl arm at positions C‐3 and C‐5 with the pyrrole groups of the central BODIPY . In addition, the peripheral BODIPYs should be contributing to increase the absorption in this spectral region even though they weakly absorbed at this UV wavelength, but owing to the number of chromophoric units linked this contribution was no longer residual and became significant.…”

Ikusgai-eremu elektromagnetiko osoan zehar igorpen sintonizagarria duten BODIPY laser-koloratzaileak

“…BODIPY koloratzaileak sintesi organikoan espezializatua den Eduardo Peña irakaslearen (Guanajuato Unibertsitatea, Mexiko) ikerkuntza-taldeak eman zizkigun (sintesiaren xehetasunak dagoeneko argitaratuta daude; BDP eta 2a [16], 2b [17] eta 1a-1b [18]). Hauen propietate fotofisikoen neurketak disoluzio diluituetan (2 · 10 -6 M) egin ziren.…”