Intriguing Physical and Chemical Properties of Phosphorus Corroles

Abstract

The fluorescence intensity of phosphorus corroles increases upon meso-aryl C-F/C-H and P-OH/P-F substitutions, the latter affects corrole-centered redox processes more than C-H/C-F substitution on the corrole's skeleton, and the presence of F atoms allows for the first experimental insight into the electronic structures of oxidized corroles. Experimental and theoretical methodologies reveal that mono- but not bis-chlorosulfonation of the corrole skeleton is under kinetic control. Selective introduction of heavy atoms leads to complexes that are phosphorescent at room temperature.

One‐Pot Synthesis of Contracted and Expanded Porphyrins with meso‐CF3 Groups

“…The slow evaporation of DCM/heptane solutions containing P(TFC)(F) 2 yielded red prismatic X‐ray quality crystals (Figure c). The average P−F and P−N distances are 1.612(2) and 1.817(3) Å, respectively, both of which are close to the two corrole structures with P−F bonds reported so far . However, unlike P(TPFC)(F) 2 and other metal chelates in this work, P(TFC)(F) 2 employs a puckered conformation like its free‐base precursor and P(TDFC)(F) 2 (TDFC=5,10,15‐tris(difluorophenyl)corrole) …”

One‐Pot Synthesis of Contracted and Expanded Porphyrins with meso‐CF3 Groups

“…Theaverage P À Fand P À Ndistances are 1.612(2) and 1.817(3) ,r espectively,b oth of which are close to the two corrole structures with PÀFb onds reported so far. [29] Thecobalt, phosphorous,and gallium chelates of (TFC) 3À and (TPFC) 3À were examined by cyclic voltammetry (Figure 4; Supporting Information, Figure S19) for uncovering the electronic effect of meso-CF 3 substituents relative to meso-C 6 F 5 groups.U nder identical conditions,t he redox potentials of the M(TFC) complexes were found to be positively shifted by 130-220 mV relative to the analogous M(TPFC) complexes (M = Co,G a, P). [29] Thecobalt, phosphorous,and gallium chelates of (TFC) 3À and (TPFC) 3À were examined by cyclic voltammetry (Figure 4; Supporting Information, Figure S19) for uncovering the electronic effect of meso-CF 3 substituents relative to meso-C 6 F 5 groups.U nder identical conditions,t he redox potentials of the M(TFC) complexes were found to be positively shifted by 130-220 mV relative to the analogous M(TPFC) complexes (M = Co,G a, P).…”

“…Theaverage P À Fand P À Ndistances are 1.612(2) and 1.817(3) ,r espectively,b oth of which are close to the two corrole structures with PÀFb onds reported so far. [29] However,u nlike P(TPFC)(F) 2 and other metal chelates in this work, P(TFC)(F) 2 employs apuckered conformation like its free-base precursor and P(TDFC)(F) 2 (TDFC = 5,10,15tris(difluorophenyl)corrole). [29] Thecobalt, phosphorous,and gallium chelates of (TFC) 3À and (TPFC) 3À were examined by cyclic voltammetry (Figure 4; Supporting Information, Figure S19) for uncovering the electronic effect of meso-CF 3 substituents relative to meso-C 6 F 5 groups.U nder identical conditions,t he redox potentials of the M(TFC) complexes were found to be positively shifted by 130-220 mV relative to the analogous M(TPFC) complexes (M = Co,G a, P).…”

“…[29] However,u nlike P(TPFC)(F) 2 and other metal chelates in this work, P(TFC)(F) 2 employs apuckered conformation like its free-base precursor and P(TDFC)(F) 2 (TDFC = 5,10,15tris(difluorophenyl)corrole). [29] Thecobalt, phosphorous,and gallium chelates of (TFC) 3À and (TPFC) 3À were examined by cyclic voltammetry (Figure 4; Supporting Information, Figure S19) for uncovering the electronic effect of meso-CF 3 substituents relative to meso-C 6 F 5 groups.U nder identical conditions,t he redox potentials of the M(TFC) complexes were found to be positively shifted by 130-220 mV relative to the analogous M(TPFC) complexes (M = Co,G a, P). This is much more than the 20 mV shift determined for the meso-esters (also relative to meso-C 6 F 5 )inthe phosphorus chelate of corrole 1-H 3 , [11] but (purely incidentally) reminiscent of the about 130 mV shift per b-pyrrole-H by b-pyrrole-CF 3 substitution in gold(III) corroles.…”

Modifications of Porphyrins and Hydroporphyrins for their Solubilization in Aqueous Media

“…On the other hand, sulfonation readily leads to the solubilization of porphyrins in aqueous media. Interestingly, the porphyrin is protonated during the sulfonation step and is thus protected by the dicationic charge from getting sulfonated at the β-positions along an electrophilic aromatic substitution pathway, in contrast with the regioselective β-sulfonation of the less basic corroles using chlorosulfonic acid [111][112][113].…”