NIR-Absorbing Tetraphenylethene-Containing bisBODIPY Nanoplatforms Demonstrate Effective Lysosome-Targeting and Combinational Phototherapy.

Photosensitizer-based phototherapies, including photodynamic therapy (PDT) and photothermal therapy (PTT), offer safe treatment modalities for tumor ablation with spatiotemporal precision. After photons are absorbed, PDT creates localized chemical damage by generating reactive oxygen species (ROS), while PTT induces localized thermal damage. However, PDT still faces hypoxic tumor challenges, while PTT encounters issues related to heat resistance and potential overheating.

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).

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.

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.

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. FeCl 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 SAr 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 O as well as O 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: NO-type Expanded BOPHY Dyes Derived from Boronic Acids.

A new family of NO-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.

β-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.