The nucleophilic substitution of aromatic moieties (SNAr) has been known for over 150 years and found wide use for the functionalization of (hetero)aromatic systems. Currently, several “types” of SNAr reactions have been established and notably the area of porphyrinoid macrocycles has seen many uses thereof. Herein, we detail the SNAr reactions of seven types of porphyrinoids with differing number and type of pyrrole units: subporphyrins, norcorroles, corroles, porphyrins, azuliporphyrins, N‐confused porphyrins, and phthalocyanines. For each we analyze the substitution dependent upon: a) the type of nucleophile and b) the site of substitution (α, β, or meso). Along with this we evaluate this route as a synthetic strategy for the generation of unsymmetrical porphyrinoids. Distinct trends can be identified for each type of porphyrinoid discussed, regardless of nucleophile. The use of nucleophilic substitution on porphyrinoids is found to often be a cost‐effective procedure with the ability to yield complex substituent patterns, which can be conducted in non‐anhydrous solvents with easily accessible simple porphyrinoids.

Chlorins that bear a gem-dimethyl group, which attributes their resistance to oxidation, are of interest for applications in photomedicine. Herein, we present the synthesis and the photophysical properties of two geminal-dimethyl chlorins (dihydroporphyrins) and their free base counterparts that act as efficient singlet oxygen generators and thus exhibit potential for use in photodynamic therapy (PDT) as anticancer or antimicrobial agents upon further derivatization. A complete characterization of their spectral and photophysical properties is accompanied by density functional calculations (DFT) as well as time dependent (TD) DFT to investigate the features of the frontier molecular orbitals. To demonstrate the potential of these compounds, standard palladium mediated reaction yielded a porphyrin-chlorin dyad in moderate yield. File list (2) download file view on ChemRxiv gemDiMeChlorin PSs ChemRxiv.pdf (1.45 MiB) download file view on ChemRxiv Supplementary -SI.pdf (2.45 MiB)

Tetraphenylethylene (TPE) and its derivatives exhibit excellent aggregation‐induced emission (AIE) properties. The TPE unit is easily accessible, and many functional groups can be introduced in a facile manner to yield effective luminescent materials in both solution and the solid‐state. It is because of this, several TPE‐based compounds have been developed and applied in many areas, such as OLEDs and chemical sensors. Boron dipyrromethenes (BODIPYs) are a class of pyrrolic fluorophore of great interest with myriad application in both material science and biomedical applications. Through the combination of Pd‐catalyzed cross‐coupling reactions and traditional dipyrromethene chemistry, we present the syntheses of novel tetra‐BODIPY‐appended TPE derivatives with different distances between the TPE and BODIPY cores. The TPE‐BODIPY arrays 6 and 9 show vastly differing AIE properties in THF/H2O systems, with 9 exhibiting dual‐AIE, along with both conjugates being found to produce singlet oxygen (1O2). We presume the synthesized BODIPY‐appended TPE scaffolds to be utilized for potential applications in the fields of light‐emitting systems and theranostics.

The goal of “personalised” medicine has seen a growing interest in the development of theranostic agents. Bifunctional, and targeted-trifunctional, theranostic water-soluble porphyrins with a histidine-like chelating group have been synthesised...