Pictet-Spengler synthesis of twisted quinoline-fused BODIPYs as heavy-atom-free photosensitizers.

Singly and doubly quinoline-fused BODIPYs were effectively synthesized through a reaction sequence consisting of the reduction of nitrophenyl-substituted BODIPYs and subsequent Pictet-Spengler cyclization. The combination of the BODIPY core and fused quinoline rings imposed significantly twisted conformations in the quinoline-fused BODIPYs (around 20.0° deviation from coplanarity obtained from X-ray crystal structure analysis). These twisted BODIPYs showed significantly reduced LUMO, redshifted absorption/emission bands, high molar extinction coefficients and satisfactory reactive oxygen species generation efficiency up to 0.56, indicating potential use as heavy-atom-free photosensitizers.

Stimulated Resonance Raman and Excited-State Dynamics in an Excitonically Coupled Bodipy Dimer: A Test for TD-DFT and the Polarizable Continuum Model.

Bodipy is one of the most versatile and studied functional dyes due to its myriad applications and tunable spectral properties. One of the strategies to adjust their properties is the formation of Bodipy dimers and oligomers whose properties differ significantly from the corresponding monomer. Recently, we have developed a novel strategy for synthesizing α,α-ethylene-bridged Bodipy dimers; however, their excited-state dynamics was heretofore unknown. This work presents the ultrafast excited-state dynamics of a novel α,α-ethylene-bridge Bodipy dimer and its monomeric parent. The dimer's steady-state absorption and fluorescence suggest a Coulombic interaction between the monomeric units' transition dipole moments (TDMs), forming what is often termed a "J-dimer". The excited-state properties of the dimer were studied using molecular excitonic theory and time-dependent density functional theory (TD-DFT). We chose the M06 exchange-correlation functional (XCF) based on its ability to reproduce the experimental oscillator strength and resonance Raman spectra. Ultrafast laser spectroscopy reveals symmetry-breaking charge separation (SB-CS) in the dimer in polar solvents and the subsequent population of the charge-separated ion-pair state. The charge separation rate falls into the normal regime, while the charge recombination is in the inverted regime. Conversely, in nonpolar solvents, the charge separation is thermodynamically not feasible. In contrast, the monomer's excited-state dynamics shows no dependence on the solvent polarity. Furthermore, we found no evidence of significant structural rearrangement upon photoexcitation, regardless of the deactivation pathway. After an extensive analysis of the electronic transitions, we concluded that the solvent fluctuations in the local environment around the dimer create an asymmetry that drives and stabilizes the charge separation. This work sheds light on the charge-transfer process in this new set of molecular systems and how excited-state dynamics can be modeled by combining the experiment and theory.

Long-Wavelength Photoconvertible Dimeric BODIPYs for Super-Resolution Single-Molecule Localization Imaging in Near-Infrared Emission.

Sulfoxide-bridged dimeric BODIPYs were developed as a new class of long-wavelength photoconvertible fluorophores. Upon visible-light irradiation, a sulfoxide moiety was released to generate the corresponding α,α-directly linked dimeric BODIPYs. The extrusion of SO from sulfoxides was mainly through an intramolecular fashion involving reactive triplet states. By this photoconversion, not only were more than 100 nm red shifts of absorption and emission maxima (up to 648/714 nm) achieved but also stable products with bright fluorescence were produced with high efficiency. The combination of photoactivation and red-shifted excitation/emission offered optimal contrast and eliminated the interference from biological autofluorescence. More importantly, the in situ products of these visible-light-induced reactions demonstrated ideal single-molecule fluorescence properties in the near-infrared region. Therefore, this new photoconversion could be a powerful photoactivation method achieving super-resolution single-molecule localization imaging in a living cell without using UV illumination and cell-toxic additives.

Synthesis, Reactivity, and Properties of a Class of π-Extended BODIPY Derivatives.

A new family of π-extended BODIPY derivatives were obtained through the condensation of aldehyde and pyrrole in aqueous solution in the presence of HCl. The new rigid π-framework extends beyond the dipyrromethene unit, which is significantly different from classical BODIPYs in the electronic configuration. Both π-extended BODIPYs displayed intense absorption and moderate emission with maxima around 565 and 620 nm, respectively, and showed interesting reactivity toward various nucleophiles. Moreover, these π-extended BODIPYs were developed as fluorescent probes for rapid and selective detection of GSH and were successfully applied for live-cell imaging.

One-Pot Access to Ethylene-Bridged BODIPY Dimers and Trimers through Single-Electron Transfer Chemistry.

A Cu(I)-promoted oxidative dimerization of BODIPY dyes was developed to give a series of α,α- ethylene-bridged BODIPY dimers and trimers for the first time. This methodology does not need harsh conditions but relies on the singlet-electron-transfer process between alkylated BODIPYs and Cu(I) salt to generate BODIPY-based radical species, which undergo a selective radical homocoupling reaction. Moreover, these resultant dimers and trimers showed high attenuation coefficients, small line widths of the absorption and emission, and intense fluorescence.

Thiophene-Fused BODIPY Dimers and Tetramers from Oxidative Aromatic Couplings as Near-Infrared Dyes.

We describe a straightforward, postmodification synthesis for a family of thiophene-fused BODIPY dimers and tetramers through transforming flexible sulfur bridges into coplanar thiophene fusions. FeCl3 was used as a bifunctional oxidant for both intramolecular and intermolecular oxidative aromatic coupling reactions. Oxidative fusion and dimerization gave strong red-shift absorptions from 509 nm for a BODIPY monomer to 830 nm for a tetramer.

Strategic Construction of Sulfur-Bridged BODIPY Dimers and Oligomers as Heavy-Atom-Free Photosensitizers.

An efficient strategy for building sulfur-bridged oligo-BODIPYs based on the SNAr reaction is described. These oligo-BODIPYs showed broadband and strong visible-near-infrared (NIR) light absorption, strong intramolecular exciton coupling, and efficient intersystem crossing (ISC). Generation of 1O2 as well as O2•- under irradiation was found to give high reactive oxygen species generation efficiencies for those oligomers.

Sterically Protected and Conformation-Restricted BOBHY Dyes with Bright Near-Infrared Fluorescence: N2O-type Expanded BOPHY Dyes Derived from Boronic Acids.

A new family of N2O-type hydrazine-containing bipyrrole boron complexes has been developed via a one-pot condensation of formylisoindole, hydrazine, and various organoboronic acids. Because of the conformation-restricted coplanar structure and the axial-substituted aryl groups, these novel dyes show deep-red absorption, bright near-infrared (NIR) fluorescence in both solution and solid states, and good solubility in organic solvents. The derivative with pyridinium ions also has been synthesized as an NIR mitochondrially targetable fluorescent probe.

Strategic Construction of Ethene-Bridged BODIPY Arrays with Absorption Bands Reaching the Near-Infrared II Region.

An efficient strategy for the controllable synthesis of BODIPY arrays based on the Stille cross-coupling reaction has been developed, from which a family of well-defined ethene-bridged BODIPY arrays from dimer to hexamer was synthesized. These arrays showed strong absorptions reaching the near-infrared II (NIR II, 1000-1700 nm) region with maxima tunable from 702 nm (dimer) to 1114 nm (hexamer) and possessed efficient light-harvesting capabilities, excellent photostability, and good photothermal conversion abilities under NIR light irradiation.

ß-AlkenylBODIPY Dyes: Regioselective Synthesis via Oxidative C-H Olefination, Photophysical Properties, and Bioimaging Studies.

A series of 2-alkenyl- and 2,6-dialkenylboron dipyrromethene (BODIPY) derivatives were synthesized through Pd(II)-catalyzed regioselective and stereoselective oxidative C-H olefination in one step. The 2-alkenyl BODIPY derivative further reacted with various amines regioselectively at the 5-position through direct oxidative nucleophilic substitution. The photophysical properties of the 2-alkenyl- and 2,6-dialkenyl-substituted BODIPYs were investigated, which showed great potential in fluorescent bioimaging.