β-Nitro-5,10,15-tritolylcorroles.
Functionalization of the β-pyrrolic positions of the corrole macrocycle with -NO(2) groups is limited at present to metallocorrolates due to the instability exhibited by corrole free bases under oxidizing conditions. A careful choice of the oxidant can limit the transformation of corroles into decomposition products or isocorrole species, preserving the corrole aromaticity, and thus allowing the insertion of nitro groups onto the corrole framework. Here we report results obtained by reacting 5,10,15-tritolylcorrole (TTCorrH(3)) with the AgNO(2)/NaNO(2) system, to give mono- and dinitrocorrole derivatives when stoichiometry is carefully controlled. Reactions were found to be regioselective, affording the 3-NO(2)TTCorrH(3) and 3,17-(NO(2))(2)TTCorrH(3) isomers as the main products in the case of mono- and disubstitution, in 53 and 20% yields, respectively. In both cases, traces of other mono- and disubstituted isomers were detected, which were structurally characterized by X-ray crystallography. The influence of the β-nitro substituents on the corrole properties is studied in detail by UV-visible, electrochemical, and spectroelectrochemical characterization of these functionalized corroles. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations of the ground and excited state properties of these β-nitrocorrole derivatives also afforded significant information, closely matching the experimental observations. It is found that the β-NO(2) substituents conjugate with the π-aromatic system of the macrocycle, which initiates significant changes in both the spectroscopic and redox properties of the so functionalized corroles. This effect is more pronounced when the nitro group is introduced at the 2-position, because in this case the conjugation is, for steric reasons, more efficient than in the 3-nitro isomer.
Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, 00133 Roma, Italy.
Manuela
M
Stefanelli
Giuseppe
G
Pomarico
Luca
L
Tortora
Sara
S
Nardis
Frank R
FR
Fronczek
Gregory T
GT
McCandless
Kevin M
KM
Smith
Machima
M
Manowong
Yuanyuan
Y
Fang
Ping
P
Chen
Karl M
KM
Kadish
Angela
A
Rosa
Giampaolo
G
Ricciardi
Roberto
R
Paolesse
D015394:Molecular Structure; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory
D011166:Porphyrins; C431863:corrole