Nicolas Desbois

Vapor-phase layer-by-layer deposition methods are capable of creating thin films of organic, inorganic, or hybrid organic–inorganic nanostructures. This approach allows the combination of the material properties of inorganic matrices with the molecular properties of organic molecules, such as building structures with optoelectronically active dye molecules. One such attractive class of dyes are the porphyrins. However, being macrocycles, their volatility is generally low, which significantly limits their use in vapor-based processes. We have therefore designed and synthesized variously substituted porphyrin macrocycles with the aim of tuning their sublimation properties, as well as their chemical reactivity, to enable their use in vapor deposition processes. A selection of these compounds has been used in molecular layer deposition (MLD) processes, proving their applicability and verifying that the porphyrin macrocycles retain their functional properties within the film material.

Fluorocorrole derivatives have been encapsulated in Tobacco mosaic virus. The resulting nanoconjugates have a high loading capacity and demonstrate in vitro antiviral activity against the vaccinia virus.

Two 3D metal–organic frameworks, based on triphenyl-corrole and its cobalt-metalated analog (CoCorr-MOF) were synthesized. CoCorr-MOF exhibited significant affinity and selectivity for CO against N ₂ , CO ₂ and O ₂ , with a CO chemisorption capacity of 7.2 cm ³ g ⁻¹ .

Here we report the optimized synthesis of pentapyrroles. We succeeded in increasing the yield for pentapyrrole PPy 1a by heating at 100 [ ]C for 4.5 h. These conditions also allowed a greater increase in the yield for PPy 1c. In contrast, with PPy 1d and 1e possessing EDGs the formation of pentapyrroles was not observed. These pentapyrroles then allowed us to access sapphyrins (e.g. cyclic analogs of pentapyrroles) by electrosynthesis. The optimized conditions for obtaining the fluorinated sapphyrins 2a and 2b involve the addition of 10 mol% TBAI (tetra-n-butylammoniom iodide), 2 eq. of TFA in CHCl₃. In comparison with classical organic synthesis, the amount of TFA was considerably reduced from 100 to 2 eq. and the oxidizing agent, [ ].[ ]. iodine, was continuously electrogenerated from the catalytic amount of TBAI used as a redox mediator.

Thanks to the presence of a phosphonic acid group, A₂B-corroles were covalently linked to the Zr clusters of a PCN-222 MOF. After insertion of Co, the cobalt corroles are able to bind CO with high selectivity vs. CO₂, N₂, and O₂.

Both the Soret and Q bands of chlorin e6 complexes blueshift on going from Zn to Pd to Pt as the coordinated metal, establishing the latter two complexes as hypsochlorins. DFT/TDDFT calculations indicate that the blueshifts appear to be related to the presence of the electronegative metal ion, which lowers the orbital energies of the HOMO and HOMO-1, while leaving the LUMOs relatively unaffected.

The high risk of CO poisoning justifies the need for indoor air quality control and warning systems based on the detection of low concentrations (ppm‐ppb) of CO. Cobalt corrole complexes selectively bind CO vs. O₂, CO₂, N₂, opening new fields of applications. By combining the CO chemisorption properties of cobalt corroles with the known sorption capacity of MOFs, we hope to obtain high performance sensing materials for CO detection. In addition, the exposed metal sites of MOFs lead to CO₂ physisorption, allowing the co‐detection of CO and CO₂. In this work, PCN‐222, a stable Zr‐based MOF made from Ni(TCPP) with natural vacancies, has been used as a porous matrix for the grafting of electron‐poor metallocorroles. The materials were characterized by powder XRD, SEM and optical microscopy, BET analyses and gas adsorption measurements at 298 K. No degradation of the crystalline structure of PCN‐222 was observed. At 1 atm, the adsorbed CO_(g) volumes measured for the best materials were 12.15 cm³ g⁻¹ and 14.01 cm³ g⁻¹ for CoCorr2@PCN‐222 and CoCorr3@PCN‐222 respectively, and both materials exhibited high CO chemisorption and selectivity against O₂, N₂, and CO₂ at low pressure due to the highest energy of the chemisorption process vs physisorption.