Structure of (R,R)-4-bromo-2-{4-[4-bromo-1-(4-toluene-sulfon-yl)-1H-pyrrol-2-yl]-1,3-di-nitro-butan-2-yl}-1-(4-toluene-sulfon-yl)-1H-pyrrole, another ostensible by-product in the synthesis of geminal-dimethyl hydro-dipyrrins.

The crystal structure of (R,R)-4-bromo-2-{4-[4-bromo-1-(4-toluene-sulfon-yl)-1H-pyrrol-2-yl]-1,3-di-nitro-butan-2-yl}-1-(4-toluene-sulfon-yl)-1H-pyrrole (1, C26H24Br2N4O8S2) is presented. The title compound was isolated in suitable yield as a by-product in our synthesis of geminal-dimethyl hydro-dipyrrins. We observe an unforeseen enanti-omeric resolution both in the bulk sample and the crystal of 1, with distinct C-H⋯O (Cmeth-yl-H⋯Onitro, Csp 3-H⋯Osulfon-yl) inter-actions observed in the enanti-omers present, along with other inter-actions, namely C5-pyrrol-yl-H⋯Osulfon-yl, forming a polymer along the crystallographic c-axis direction. Whilst pyrrolic fragments are well documented in the literature, little data is found surrounding the 1,3-di-nitro-butane scaffold.

Structures of S-(pyridin-2-yl) 4-nitro-benzo-thio-ate, S-(pyridin-2-yl) 4-methyl-benzo-thio-ate and S-(pyridin-2-yl) 4-meth-oxy-benzo-thio-ate: building blocks for low-symmetry multifunctional tetra-pyrroles.

The crystal structures of three S-(pyridin-2-yl) benzo-thio-esters with varying para-phenyl substituents are presented, namely, S-(pyridin-2-yl) 4-nitro-benzo-thio-ate (1, C12H8N2O3S), S-(pyridin-2-yl) 4-methyl-benzo-thio-ate (2, C13H11NO2S) and S-(pyridin-2-yl) 4-meth-oxy-benzo-thio-ate (3, C13H11NO2S). This class of compounds are used in the mono-acyl-ation of pyrrolic species to yield multifunctional tetra-pyrroles. The structures presented herein are the first of their compound class. The dominant inter-actions present in this series are π-π stacking and C-H⋯O inter-actions, and as the para-phenyl motif changes from electron withdrawing (NO2, 1) to electron donating (OCH3, 3), changes are observed in the inter-actions present in the crystal packing, from predominant π-π stacking in 1 to exclusively C-H⋯O/N inter-actions (Car-yl-H⋯Ocarbon-yl, C-H⋯Ometh-oxy and Car-yl-H⋯Npyridine) in 3.

Synthesis and Properties of BODIPY Appended Tetraphenylethylene Scaffolds as Photoactive Arrays.

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.

Crystal structures of 4-bromo-2-formyl-1-tosyl-1H-pyrrole, (E)-4-bromo-2-(2-nitro-vin-yl)-1-tosyl-1H-pyrrole and 6-(4-bromo-1-tosyl-pyrrol-2-yl)-4,4-dimethyl-5-nitro-hexan-2-one.

The crystal structures of three inter-mediate compounds in the synthesis of 8-bromo-2,3,4,5-tetra-hydro-1,3,3-tri-methyl-dipyrrin are reported; 4-bromo-2-formyl-1-tosyl-1H-pyrrole, C12H10BrNO3S, (E)-4-bromo-2-(2-nitro-vin-yl)-1-tosyl-1H-pyrrole, C13H11BrN2O4S, and 6-(4-bromo-1-tosyl-pyrrol-2-yl)-4,4-dimethyl-5-nitro-hexan-2-one, C19H23BrN2O5S. The compounds show multitudinous inter-molecular C-H⋯O inter-actions, with bond distances and angle consistent in the series and within expectations, as well as varied packing types. The merits of collecting data beyond the standard resolution usually reported for small mol-ecules are discussed.

Nucleophilic Aromatic Substitution (SNAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects.

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, ß, 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.

Synthesis of a porphyrin with histidine-like chelate: an efficient path towards molecular PDT/SPECT 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 via copper-catalysed azide-alkyne cycloaddition (CuAAC) "click" chemistry in high yield and purity. They are capable of photodynamic treatment and [99mTc(CO)3]+ complexation for single-photon emission computed tomography (SPECT) imaging, with a radiochemical yield of >95%. The toxicity and phototoxicity were evaluated on HT-29 cells, DU145, and DU145-PSMA cell lines, with the targeted theranostic showing more potent phototoxicity towards DU145-PSMA expressing cells.