Acid-catalyzed condensation of pyrrole, 4-trifluoromethylbenzaldehyde, and azulene, followed by DDQ oxidation, has resulted in the isolation of the novel macrocycle azulicorrole, arguably the first example of a carbacorrole aside from N-confused corrole. Despite poor yields (<1%), the free ligand could be structurally characterized and converted to the formal Cu(III) and Au(III) derivatives, of which the Cu(III) complex could also be structurally characterized. Both the free base and the two metal complexes exhibit richly structured UV-vis spectra that extend well into the near-infrared, suggesting potential applications in bioimaging and photodynamic therapy.

Six-coordinate iridium(III) triarylcorrole derivatives, Ir[TpXPC)]L₂, where TpXPC = tris(para-X-phenyl)corrole (X = CF₃, H, Me, and OCH₃) and L = pyridine (py), trimethylamine (tma), isoquinoline (isoq), 4-dimethylaminopyridine (dmap), and 4-picolinic acid (4pa), have been examined, with a view to identifying axial ligands most conducive to near-infrared phosphorescence. Disappointingly, the phosphorescence quantum yield invariably turned out to be very low, about 0.02 - 0.04% at ambient temperature, with about a two-fold increase at 77 K. Phosphorescence decay times were found to be around ~5 µs at 295 K and ~10 µs at 77 K. Fortunately, two of the Ir[TpCF₃PC)]L₂ derivatives, which were tested for their ability to sensitize singlet oxygen formation, were found to do so efficiently with quantum yields Φ(¹O₂) = 0.71 and 0.38 for L = py and 4pa, respectively. Iridium corroles thus may hold promise as photosensitizers in photodynamic therapy (PDT). The possibility of varying the axial ligand and of attaching biotargeting groups at the axial positions makes iridium corroles particularly exciting as PDT drug candidates.

As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β-perhalogenation of five ReO meso-tris(para-X-phenyl)corroles, Re[TpXPC](O) (X = CF₃, H, F, CH₃, and OCH₃), with elemental chlorine and bromine. With Cl₂, β-octachlorinated products Re[Cl₈TpXPC](O) were rapidly obtained for X = CF₃, H, and CH₃, but X = OCH₃ resulted in overchlorination on the meso-aryl groups. Full β-octabromination proved slower relative to Cu and Ir corroles, but the desired Re[Br₈TpXPC](O) products were finally obtained for X = H and F after a week at room temperature. For X = CH₃ and OCH₃, these conditions led to undecabrominated products Re[Br₁₁TpXPC](O). Compared to the β-unsubstituted starting materials, the β-octahalogenated products were found to exhibit sharp ¹H NMR signals at room temperature, indicating that the aryl groups are locked in place by the β-halogens, and substantially redshifted Soret and Q bands. Single-crystal X-ray structures of Re[Cl₈TpCF₃PC](O), Re[Cl₈TpCH₃PC](O), and Re[Br₈TpFPC](O) revealed mild saddling for one Cl₈ structure and the Br₈ structure. These structural variations, however, appear too insignificant to explain the slowness of the β-octabromination protocols, which seems best attributed to the deactivating influence of the high-valent Re center.

Ring-opening of furans at the equatorial methylene bridge positions of a calix[4]arene gives access to a range of new molecules (in good yield) that have widespread potential impact in supramolecular chemistry amongst other areas.

Air pollution by nitrogen oxides, NO_x, is a major problem, and new capture and abatement technologies are urgently required. Here, we report a metal-organic framework (Manchester Framework Material 520 (MFM-520)) that can efficiently confine dimers of NO₂, which results in a high adsorption capacity of 4.2 mmol g^-1 (298 K, 0.01 bar) with full reversibility and no loss of capacity over 125 cycles. Treatment of NO₂@MFM-520 with water in air leads to a quantitative conversion of the captured NO₂ into HNO₃, an important feedstock for fertilizer production, and fully regenerates MFM-520. The confinement of N₂O₄ inside nanopores was established at a molecular level, and the dynamic breakthrough experiments using both dry and humid NO₂ gas streams verify the excellent stability and selectivity of MFM-520 and confirm its potential for precious-metal-free deNO_x technologies.

Emissions of SO₂ from flue gas and marine transport have detrimental impacts on the environment and human health, but SO₂ is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO₂ in a porous material, [Cu₂(L)] (H₄L = 4',4‴-(pyridine-3,5-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO₂ uptake of 17.5 mmol g^-1 at 298 K and 1.0 bar, and the SO₂ binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO₂ to open Cu(II) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO₂ binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO₂ from simulated flue gas mixtures, as confirmed by breakthrough experiments.