Synthesis, spectroscopic/electrochemical characterization and DNA interaction study of novel ferrocenyl‐substituted porphyrins

Abstract

We report the synthesis and characterization of two new mesoferrocenylporphyrins, with the ferrocenyl unit attached at the para position of a C 6 F 4 group by a C-N bond with -NH(CH 2 ) 2 NH-(2a) and -NH(CH 2 ) 4 NH-(2b) spacers. Compounds 2a and 2b were characterized through elemental analyses, electrospray ionization high-resolution mass spectrometry, 1 H NMR, UV-visible and fluorescence spectroscopies, electrochemistry and spectroelectrochemistry. The free base porphyrin 2 was included for comparison purposes. The binding ability of 2 and the porphyrin derivatives 2a and 2b with calf thymus DNA was determined using UV-visible and fluorescence spectroscopies. The results suggest that the interaction of these systems most probably occurs through π-stacking by non-classical modes involving the partial insertion of the C 6 F 5 ring between adjacent base pairs on DNA and possible hydrogen interaction with the aliphatic -NH(CH 2 ) n NH-(n = 2 or 4) groups with calf thymus DNA. Moreover, we also demonstrate that porphyrins generate singlet oxygen species and show good photostability after irradiation.

A New Protocol for the Synthesis of New Thioaryl-Porphyrins Derived from 5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin: Photophysical Evaluation and DNA-Binding Interactive Studies

“…Furthermore, the changes in intensity of the π→π* Soret transition may be due to the interaction of the aromatic structure of the tetrapyrrolic derivatives, peripheral groups, or both, which is likely because of H-bonding interactions with the DNA nucleobases. This effect is probably caused by the presence of the π-density macrocycle moiety in the structure that may interact with DNA via hydrophobic interactions, as previously reported for some cases of porphyrin derivatives, and possibly by H-bonding interactions [ 32 , 43 ].…”

“…By inserting the aryl-sulfur units with different electronic groups at the para -position of the meso -aryl moieties, the fluorescence quantum yield decreased when compared to the TPP standard. This may be explained by the presence of the halogen atoms in the meso -aryl moieties [ 32 ]. Moreover, the spin-orbit coupling factor of the halogen atoms decreased radiative channels and increased non-radiative channel processes [ 32 , 33 , 34 ].…”

Iron and Ruthenium Glycoporphyrins: Active Catalysts for the Synthesis of Cyclopropanes and Aziridines

“…The direct reaction of cellobioside 1 with either F 5 TPPH 2 or F 20 TPPH 2 porphyrin afforded glycoporphyrins 2 and 3 in 60 % and 40 % yields, respectively (Scheme ). From a synthetic point of view, the presence of one or four C 6 F 5 meso substituents allowed the anchoring of the desired number (one or four) of carbohydrate units onto the porphyrin skeleton by a nucleophilic substitution of the para fluorine atom of the C 6 F 5 moiety.…”

“…Reagents . Organic azides, diazo compounds, meso ‐tetrakis(pentafluorophenyl)porphyrin ( F 20 TPPH 2 ), 5‐(pentafluorophenyl)‐10,15,20‐triphenylporphyrin ( F 5 TPPH 2 ), methyl 2,3,6‐tri‐O‐benzyl‐4‐O‐(2,3,6‐tri‐O‐benzyl‐β‐ d ‐glucopyranosyl)‐β‐ d ‐glucopyranoside ( 1 ), α‐5,10‐β‐15,20‐tetrakis(2‐[(3‐chloromethyl)benzoylamido]phenyl) porphyrin ( 5 ), methyl 2,3,6‐tri‐O‐benzyl‐4‐O‐(prop‐2‐ynyl)‐ α‐ d ‐glucopyranoside ( 6 ), Ru(F 20 TPP)(CO) were synthesized as reported in literature. Other starting materials have been purchased and used as received.…”

Valorization of CO2 into N‐alkyl Oxazolidin‐2‐ones Promoted by Metal‐Free Porphyrin/TBACl System: Experimental and Computational Studies

“…Acetone was distilled over calcium sulfate and kept under nitrogen. meso‐ Tetrakis phenyl porphyrin (TPPH 2 ), [23] 5‐(pentafluorophenyl)‐10,15,20‐triphenyl porphyrin (F 5 TPPH 2 ), [24] meso ‐tetrakis(pentafluorophenyl) porphyrin (F 20 TPPH 2 ), [25] octaethylporphyrin (OEPH 2 ), [26] meso ‐tetrakis(4‐trifluoromethylphenyl) porphyrin (4‐CF 3 TPPH 2 ), [27] meso ‐tetrakis(4‐tert‐butylphenyl) porphyrin (4‐ t BuTPPH 2 ), [28] meso ‐tetrakis(4‐carboxyphenyl) porphyrin (4‐COOHTPPH 2 ) [29] and 5‐(2‐(3‐bromopropoxy)phenyl)‐10,15,20‐trispentafluorophenylporphyrin ( 10 ) [22] were all synthesized following reported procedures. 1‐(3,5‐ bis ‐Trifluoromethylphenyl)‐2‐phenylaziridine [30] and all the N ‐alkyl aziridines were synthesized following reported procedure [18a] .…”