Preparation of group 15 (phosphorus, antimony, and bismuth) complexes of meso-tetra-p-tolylporphyrin (TTP) and x-ray crystal structure of [Sb(TTP)(OCH(CH3)2)2]Cl

Phenanthriporphyrin: An Antiaromatic Aceneporphyrinoid as a Ligand for a Hypervalent Organophosphorus(V) Moiety

“…Significantly, 4-P(OMe) 2 conserves the paratropicity of 4-H 3 as is reflected by the 1 HNMR spectrum which demonstrated at ypical pattern for an antiaromatic porphyrinoid ( Figure 5). Consistent with coordination, the signals attributable to H (22,25) and NH in 4-H 3 disappear in the spectrum of 4-P(OMe) 2 .The doublet at d = 6.63 ppm assigned to methoxy ligands ( 3 J P-H = 21.2 Hz) is relocated downfield as compared to trimethyl phosphate OP(OMe) 3 (d = 3.78 ppm) reflecting the paratropicity of 4-P(OMe) 2 .I nt he 31 PNMR spectrum, a 31 Presonance signal, attributable to the inserted phosphorus(V), appears at d = À137.1 ppm, avalue which approaches the d = À160-À230 ppm range which is characteristic for phosphorus(V) porphyrins. [31] The 31 PNMR spectrum collected without 1 Hdecoupling showed as eptet as ar esult of the coupling of the 31 Pcenter with six equivalent protons of the two apical methoxy groups ( Figure 5, inset B).…”

“…Consistent with coordination, the signals attributable to H (22,25) and NH in 4-H 3 disappear in the spectrum of 4-P(OMe) 2 .The doublet at d = 6.63 ppm assigned to methoxy ligands ( 3 J P-H = 21.2 Hz) is relocated downfield as compared to trimethyl phosphate OP(OMe) 3 (d = 3.78 ppm) reflecting the paratropicity of 4-P(OMe) 2 .I nt he 31 PNMR spectrum, a 31 Presonance signal, attributable to the inserted phosphorus(V), appears at d = À137.1 ppm, avalue which approaches the d = À160-À230 ppm range which is characteristic for phosphorus(V) porphyrins. [31] The 31 PNMR spectrum collected without 1 Hdecoupling showed as eptet as ar esult of the coupling of the 31 Pcenter with six equivalent protons of the two apical methoxy groups ( Figure 5, inset B). In fact 31 To link together acenes and suitable porphyrinoids motifs, we employed af ormal conversion of [18]tetraphyrin(1.1.1.0) through the hypothetical A,D-di-m-benziporphyrin(1.1.1.0) into phenanthriporphyrin-a hybrid macrocycle combining the structural features of polycyclic aromatic hydrocarbons and porphyrins.T he nature of the connection between the two formal parts of the macrocycle results in its distinct antiaromatic character which is preserved after protonation.…”

“…[31] The 31 PNMR spectrum collected without 1 Hdecoupling showed as eptet as ar esult of the coupling of the 31 Pcenter with six equivalent protons of the two apical methoxy groups ( Figure 5, inset B). In fact 31 To link together acenes and suitable porphyrinoids motifs, we employed af ormal conversion of [18]tetraphyrin(1.1.1.0) through the hypothetical A,D-di-m-benziporphyrin(1.1.1.0) into phenanthriporphyrin-a hybrid macrocycle combining the structural features of polycyclic aromatic hydrocarbons and porphyrins.T he nature of the connection between the two formal parts of the macrocycle results in its distinct antiaromatic character which is preserved after protonation. Theunique coordination core of 4-H 3 consists of two carbon and two nitrogen donors that can be activated toward coordination.…”

Lead structures for applications in photodynamic therapy. 5. Synthesis and biological evaluation of water soluble phosphorus(V) 5,10,15,20-tetraalkylporphyrins for PDT

“…Here, we present the use of P(V) porphyrin complexes which offer such a possibility, as they allow not only the preparation of new drug candidates but simple improvements of existing drugs through P(V) complexation, i.e., water solubility [18], better uptake and potentially less side effects. P(V) porphyrin complexes are known but their exploitation in terms of PDT has been limited thus far [18,19,20,21,22,23,24,25]. We found that through P(V) complexation of simple meso tetrasubstituted porphyrins both the water solubility and the in vitro cytotoxicity of the photosensitizer can be drastically improved with respect to the non-complexed form.…”

“…Meso aryl and β-octaethyl P(V) porphyrins have been prepared before, mostly for coordination studies, redox chemistry investigations, and structural analyses [19,20,21,22,23,24]. The procedure we adopted followed that developed for P(V) insertion of 2,3,7,8,12,13,17,18-octaethylporphyrin derivatives, whereby PCl 3 acts as a more effective reagent for insertion over POCl 3 due to a lower phosphorus oxidation state [23,24].…”