Synthesis, X-structure and solvent induced electronic states tuning of meso-tris(4-nitrophenyl)corrolato-copper complex

Bhattacharya, Dibyendu; Singh, Pinky; Sarkar, Sabyasachi

doi:10.1016/j.ica.2010.07.016

Cited by 21 publications

(29 citation statements)

References 43 publications

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“…The invariant values of E 1/2 for the reversible one-electron reduction of meso -nitrophenyl groups on earlier studied metallomacrocycles in CH 2 Cl 2 , PhCN, or pyridine suggest the lack of an interaction between these redox-active units on the meso positions of the different compounds, be it a porphyrin, a corrole, or another related conjugated system. ,,,,,,− An electronic interaction between the three nitrophenyl groups across the macrocycle is also not electrochemically observed in the currently studied compounds 3 and 4 , which both contain three nitrophenyl groups. As shown in Table and Figure , the meso -(4-F-3-NO 2 )Ph group on compound 1 is reversibly reduced by one electron at −1.10 to −1.14 V in the three solvents, and essentially the same value of E 1/2 is seen in the cyclic voltammogram of compound 3 , which contains a single (4-F-3-NO 2 )Ph group at the 10 position of the macrocycle and two p -NO 2 Ph groups at the 5 and 15 positions (see Chart ).…”

Section: Resultsmentioning

confidence: 82%

“…Although the half-wave potentials for reduction of the nitrophenyl groups on different metallomacrocycles do not depend upon the specific macrocycle or the specific central metal ion, these substituents do exert a moderate-to-strong electron-withdrawing effect on other redox reactions of the compounds, shifting their potentials in a positive direction by 45–90 mV per NO 2 Ph group in the case of porphyrins and by 35–100 mV in the case of corroles. ,, The first oxidation of the currently investigated compounds 1 – 4 exhibits a 76 mV potential shift per NO 2 Ph group in pyridine and a 80 mV shift per NO 2 Ph group in CH 2 Cl 2 , as shown in Figure .…”

Section: Resultsmentioning

confidence: 95%

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Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

et al. 2018

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A series of bis(pyridine)cobalt corroles with one or three nitrophenyl groups on the meso positions of the corrole macrocycle were synthesized and characterized as to their electrochemical and spectroscopic properties in dichloromethane, benzonitrile, and pyridine. The potentials for each electrode reaction were measured by cyclic voltammetry and the electron-transfer mechanisms evaluated by analysis of the electrochemical data combined with UV-visible spectra of the neutral, electroreduced, and electroxidized forms of the corroles. The proposed electronic configurations of the initial compounds and the prevailing redox reactions involving the electroactive central cobalt ion, the electroactive conjugated macrocycle, and the electroactive meso-nitrophenyl groups are all discussed in terms of solvent binding and the number of the nitrophenyl groups and other substituents on the meso-nitrophenyl rings of the compounds.

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Section: Resultsmentioning

confidence: 82%

Section: Resultsmentioning

confidence: 95%

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

et al. 2018

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“…Corrole absorption spectra (and also a number of other physical and chemical properties) are also prone to significant solvatochromic effects that were described and rationalized before. Thus, for both corroles a significant redshift of the Q band region is observed in the strongly polar solvent ACN relative to the nonpolar solvent DCM.…”

Section: Resultsmentioning

confidence: 82%

A Spectroscopic and Theoretical Investigation of a Free‐Base meso‐Trithienylcorrole

Greco

Rossi

Birge

et al. 2013

Photochem & Photobiology

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The unique optical properties of free-base meso-trithienylcorrole were compared to those of the widely investigated meso-triphenyl-substituted analogue. A combination of spectroscopic and computational experiments were undertaken to elucidate the relationship between structural features of the neutral, mono-anionic, and mono-cationic forms of the corroles and their corresponding optical properties. A general bathochromic shift was measured for the thienyl-substituted corrole. The experimental spectra are supported by excited state calculations. A systematic series of ground state minimizations were performed to determine energy minima for the flexible and solvent-sensitive molecules. Trithienylcorrole was found to have a more non-planar macrocycle in conjunction with a high degree of π-overlap with the meso-substituents. Both structural features contribute to their bathochromically shifted optical spectra. The configurational character of the thienyl-substituted corrole is shown to have a larger degree of molecular orbital mixing and doubly excited character, which suggest a more complex electronic structure that does not fully adhere to the Gouterman four-orbital model. The reactivity of the thienyl groups, particularly with respect to their ability to be (electro)-polymerized, combined with the tight coupling of the meso-thienyl groups with the corrole chromophore elucidated in this work, recommends the meso-thienylcorroles as building blocks in, for instance, organic semiconductor devices.

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“…1 and 2. A single multi-electron reduction of meso- C 6 H 4 NO 2 groups has previously been reported for copper triarylcorroles 39 as well as for tetraphenylporphyrins having the same electroactive substituents at the four meso -positions of the macrocycle. 34, 35 …”

Section: Resultsmentioning

confidence: 90%

β-Nitro Derivatives of Iron Corrolates

et al. 2012

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Two different methods for the regioselective nitration of different meso-triarylcorroles leading to the corresponding β-substituted nitrocorrole iron complexes have been developed. A two-step procedure affords three Fe(III) nitrosyl products - the unsubstituted corrole, the 3-nitrocorrole and the 3,17-dinitrocorrole. In contrast, a one-pot synthetic approach drives the reaction almost exclusively to formation of the iron nitrosyl 3,17-dinitrocorrole. Electron-releasing substituents on the meso-aryl groups of the triarylcorroles induce higher yields and longer reaction times than what is observed for the synthesis of similar triarylcorroles with electron-withdrawing functionalities, and these results can be confidently attributed to the facile formation and stabilization of an intermediate iron corrole π-cation radical. Electron-withdrawing substituents on the meso-aryl groups of triarylcorrole also seem to labilize the axial nitrosyl group which, in the case of the pentafluorophenylcorrole derivative, results in the direct formation of a disubstituted iron μ-oxo dimer complex. The influence of meso-aryl substituents on the progress and products of the nitration reaction was investigated. In addition, to elucidate the most important factors which influence the redox reactivity of these different iron nitrosyl complexes, selected compounds were examined by cyclic voltammetry and thin-layer UV-visible or FTIR spectroelectrochemistry in CH2Cl2.

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Synthesis, X-structure and solvent induced electronic states tuning of meso-tris(4-nitrophenyl)corrolato-copper complex

Cited by 21 publications

References 43 publications

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

Electrochemistry of Bis(pyridine)cobalt (Nitrophenyl)corroles in Nonaqueous Media

A Spectroscopic and Theoretical Investigation of a Free‐Base meso‐Trithienylcorrole

β-Nitro Derivatives of Iron Corrolates

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