63160-31-6Relevant articles and documents
Synthetic access to new porphyrinoids from 2-nitro-5,10,15,20-tetraphenylporphyrin and an arylacetonitrile
Amiri, Ouafa,Moura, Nuno M. M.,Faustino, Maria A. F.,Cavaleiro, José A. S.,Rakib, El Mostapha,Neves, Maria G. P. M. S.
, p. 67 - 75 (2019)
Abstract: In this work, the reactivity of 2-nitro-5,10,15,20-tetraphenylporphyrin with 2-(4-nitrophenyl)acetonitrile in the presence of KOH as base was studied. Under these conditions, three new compounds were isolated: a β-di-substituted derivative, as the major compound, accompanied by two minor products, a π-extended and a β-isoxazoline-fused derivative, all in acceptable yields. A preliminary study was also performed in the presence of K2CO3. It allowed the isolation of a cyclopropyl-annulated chlorin in very good yield. All the obtained products were photochemically and photophysically characterized, some of them showing promising properties to be used as photosensitizers in photodynamic processes. Graphical abstract: [Figure not available: see fulltext.].
Synthesis and properties of bis-porphyrin molecular tweezers: Effects of spacer flexibility on binding and supramolecular chirogenesis
Blom, Magnus,Norrehed, Sara,Andersson, Claes-Henrik,Huang, Hao,Light, Mark E.,Bergquist, Jonas,Grennberg, Helena,Gogoll, Adolf
, (2016/02/05)
Ditopic binding of various dinitrogen compounds to three bisporphyrin molecular tweezers with spacers of varying conformational rigidity, incorporating the planar enediyne (1), the helical stiff stilbene (2), or the semi-rigid glycoluril motif fused to the porphyrins (3), are compared. Binding constants Ka = 104-106 M-1 reveal subtle differences between these tweezers, that are discussed in terms of porphyrin dislocation modes. Exciton coupled circular dichroism (ECCD) of complexes with chiral dinitrogen guests provides experimental evidence for the conformational properties of the tweezers. The results are further supported and rationalized by conformational analysis.
Reaction of metallo-2-nitro-5,10,15,20-tetraphenylporphyrins with oxyanions. Temperature-dependent competition between nucleophilic addition and single-electron transfer processes
Crossley, Maxwell J.,King, Lionel G.
, p. 1251 - 1260 (2007/10/03)
The outcome of the reaction of metallo-2-nitro-5,10,15,20-tetraphenylporphyrins with oxyanions is dependent both on the nature of the coordinated metal ion and on the reaction temperature, Metallo-2-nitro-5,10,15,20-tetraphenylporphyrins with relatively electronegative chelated metal ions (CuII, NiII and FeIIICl) react with methoxideionin N,N-dimethylformamide to afford mainly the corresponding metallated 2-methoxy-3-nitroporphyrins and 2,2-dimethoxy-3-nitro-2,3-dihydroporphyrins. The zincII chelate 7 is unreactive towards methoxide under identical conditions. When the room temperature reaction of (2-nitro-5,10,15,20-tetraphenylporphyrinato)nickel(II) 5 with methoxide is quenched with water after 1 min, the trans-(2-methoxy-3-nitro-2,3-dihydroporphyrinato)nickel(II) 14 is obtained. Inclusion of nitrobenzene in the reaction of the copper(II) chelate 4 with methoxide is beneficial and results in the formation of the 2,2-dimethoxy-3-nitro-2,3-dihydroporphyrin 8 in 90% yield. Reaction of 4 with benzyl oxide ion gives analogous products but in lower yield, while the major product from reaction of 4 with hydroxide ion is the 2-hydroxy-3-nitroporphyrin 16. At elevated temperatures the nature of the reaction of the copper(II) chelate 4 with methoxide changed to afford the corresponding copper(II) 2-alkoxyporphyrin 10 and the denitrated parent porphyrin 20; the later compounds arise from radical reactions. A mechanistic rationale for the processes involved in these temperature-dependent reactions is presented. The ease with which these reactions occur is a consequence of the fact that all the reaction intermediates are able to retain macrocyclic aromaticity.
