Fully Functionalizable β,β′-BODIPY Dimer: Synthesis, Structure, and Photophysical Signatures

Abstract

The versatility in the synthesis of BODIPY derivatives in terms of functionalization is further demonstrated. In particular, in this work β-β'-BODIPY dimers with varied functional groups in the meso positions were synthesized in very efficient yields and short reaction times from a single platform. A photophysical study was carried out in all of the compounds. The resultant dimers show absorption bands at around 600 nm as a consequence of electronically coupled monomers disposed with a dihedral angle of around 30°, which is supported by theoretical simulations. The emission properties of these molecules are distinguished by the appearance of an ICT state as the polarity of the solvent increases.

Decorating BODIPY with Electron‐Withdrawing NO Group: Spectroelectrochemical Consequences and Computational Investigation

“…Three further peaks are also observed at higher energy, corresponding to wavelengths of 440, 374 and 322 nm, with an additional UV peak at 267 nm. As for 2 , some higher energy bands are related to the presence of the nitrosyl group, as shown for nitrosobenzene derivatives [47–49] . Similar behaviour is seen for 3 in MeCN solution (see Figure S9 in the Supplementary Information).…”

“…Over the time‐course of electrolysis, one band at the visible region with a maximum at 560 nm was observed, together with a decrease in the intensity of the strongly absorbing band (Figure 7). Prior to the onset of the electrolysis, little, if any, absorption above 550 nm exists, which suggests that these two peaks indicate the presence of a new solution phase species, possibly the nitroso radical anion, as observed previously [47–48] …”

“…We suggest that this significant deviation in the absorption spectra for 2 and 3 compared with 1 corresponds to the dimerization process indicated by the voltammetric data described in section 3.1.1 above. Indeed, it is often assumed that the azodioxy dimer (Figure 5) does not absorb at the wavelength corresponding to the monomeric main peak [48] . Thus, taken together, this suggests that the extent of the monomer/azodioxy dimer equilibrium for 2 and 3 in DMF is greatest for 3 , but is still important for 2 .…”

Palladium(II)-Catalyzed Dehydrogenative Strategy for Direct and Regioselective Oligomerization of BODIPY Dyes

“…The second one is the cross-coupling method, which often relies on classical Suzuki–Miyaura reactions between halogenated BODIPYs and β-boryl BODIPY (Figure a). The key β-boryl BODIPY was used to couple to various halogenated BODIPYs to generate the corresponding β,β- or α,β-dimers and trimers (Figure a) . The last one, the oxidative homocoupling of BODIPY, is one of the most straightforward and practical methods for BODIPY and oligomers.…”

Tuning the Photonic Behavior of Symmetrical bis-BODIPY Architectures: The Key Role of the Spacer Moiety

“…Toward this aim, boron-dipyrromethene (BODIPY) scaffolds, e.g., 1 in Figure 1, are ideal candidates as building blocks owing to the chemical versatility of the chromophoric core (Loudet and Burgess, 2007; Ulrich et al, 2008). The boron-dipyrrin backbone is ready amenable to a wide range of post-functionalization routes (Boens et al, 2015), which might allow its ulterior covalent linkage to additional chromophoric units (Dumas-Verdes et al, 2010; Misra et al, 2014; Gartzia-Rivero et al, 2015; Kesavan et al, 2015; Arroyo-Córdoba et al, 2018; Xu et al, 2018; Zhang et al, 2018). Such tailoring of the molecular structure being available enables the modulation of the spectral bands of the BODIPY, leading to stable and bright dyes along the whole visible spectrum and even reaching the near-infrared region (Lu et al, 2014; Bañuelos, 2016).…”