Metal Complexes of Singly, Doubly and Triply Linked Porphyrins and Corroles: An Insight into the Physicochemical Properties

Hazari, Arijit Singha; Chandra, Sudeshna; Kar, Sanjib; Sarkar, Biprajit

doi:10.1002/chem.202104550

Cited by 15 publications

(14 citation statements)

References 140 publications

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“… Differences in self-consistent charge density calculated for the COT-fused Fe(III) corrole dimer, relative to the state with one less electron. Iso-surface value of 0.001 electrons/bohr 3 was used. Electron’s addition and removal energies are in eV.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Conjugated arrays based on porphyrins, and to a lesser extent corroles, have been receiving much attention owing to their attractive electronic, − optical, − and electrochemical , properties. One area of focus is the development of synthetic strategies for various modes of conjugation, which may be classified by the number of C atoms involved in each of the chromophores: bridging by π-conducting moieties that link , one meso -C atom; 8-membered ring formation by using two β-pyrrole C atoms; − heavily fused derivatives in which 4 C atoms are involved (Figure ).…”

Section: Introductionmentioning

confidence: 99%

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Electronic Coupling and Electrocatalysis in Redox Active Fused Iron Corroles

et al. 2022

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Conjugated arrays composed of corrole macrocycles are increasingly more common, but their chemistry still lags behind that of their porphyrin counterparts. Here, we report on the insertion of iron(III) into a β,β-fused corrole dimer and on the electronic effects that this redox active metal center has on the already rich coordination chemistry of [H3tpfc] COT, where COT = cyclo-octatetraene and tpfc = tris(pentafluorophenyl)corrole. Synthetic manipulations were performed for the isolation and full characterization of both the 5-coordinate [FeIIItpfc(py)]2COT and 6-coordinate [FeIIItpfc(py)2]2COT, with one and two axial pyridine ligands per metal, respectively. X-Ray crystallography reveals a dome-shaped structure for [FeIIItpfc(py)]2COT and a perfectly planar geometry which (surprisingly at first) is also characterized by shorter Fe–N (corrole) and Fe–N (pyridine) distances. Computational investigations clarify that the structural phenomena are due to a change in the iron(III) spin state from intermediate (S = 3/2) to low (S = 1/2), and that both the 5- and 6-coordinated complexes are enthalpically favored. Yet, in contrast to iron(III) porphyrins, the formation enthalpy for the coordination of the first pyridine to Fe(III) corrole is more negative than that of the second pyridine coordination. Possible interactions between the two corrole subunits and the chelated iron ions were examined by UV–Vis spectroscopy, electrochemical techniques, and density functional theory (DFT). The large differences in the electronic spectra of the dimer relative to the monomer are concluded to be due to a reduced electronic gap, owing to the extensive electron delocalization through the fusing bridge. A cathodic sweep for the dimer discloses two redox processes, separated by 230 mV. The DFT self-consistent charge density for the neutral and cationic states (1- and 2-electron oxidized) reveals that the holes are localized on the macrocycle. A different picture emerges from the reduction process, where both the electrochemistry and the calculated charge density point toward two consecutive electron transfers with similar energetics, indicative of very weak electron communication between the two redox active iron(III) sites. The binuclear complex was determined to be a much better catalyst for the electrochemical hydrogen evolution reaction (HER) than the analogous mononuclear corrole.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electronic Coupling and Electrocatalysis in Redox Active Fused Iron Corroles

et al. 2022

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“…The existence of organic ligands on the support surface can facilitate the anchoring of metal ions/metals via chelation 31,32 The properties of ligands complexed with the metals may also regulate the activity and selectivity of the catalyst 33,34 . In bimetallic complexes, bridging ligands can be crucial in metal-metal interactions [35][36][37][38][39] . According to the through-bond superexchange formalism, bridging ligands with π-conjugated structures are favored for accelerating electron transfer 40 .…”

Section: Introductionmentioning

confidence: 99%

Conjugated Cu-Ni bimetallic complex supported on Fe 3 O 4 @SiO 2 : An efficient nanocatalyst with synergistic performance for the solvent-free Sonogashira, and C-N cross-couplings

Nasseri

Kassaee

et al. 2023

Preprint

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Synthesis of a novel Cu-Ni bimetallic system comprising magnetic nanoparticles as the core and 4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole (4-ABPT) as a conjugated bridge between nickel and copper species is described. With low Cu and Ni loading (0.06 mol% Ni, 0.08 mol% Cu), the resulting Fe3O4@SiO2@4-ABPT/Cu-Ni is discovered to be a highly efficient catalyst for the Sonogashira and C-N cross-coupling reactions. It is well characterized by FT-IR, XRD, EDX, FE-SEM, TEM, ICP, VSM, TGA/DTG/DTA, and XPS techniques. Fe3O4@SiO2@4-ABPT/Cu-Ni as a nanocatalyst in the Sonogashira and C-N cross-coupling reactions is compatible with a wide range of amines and aryl halides and gives desired coupling products in high to excellent yields under palladium- and solvent-free conditions. The XPS results show that the 4-ABPT as a ligand can adjust electron transfer between Ni and Cu in Fe3O4@SiO2@4-ABPT/Cu-Ni, which promotes the formation and stabilization of Cu+ and Ni3+ species. Electronic interactions and the synergistic effect between these metals increase the selectivity and activity of Fe3O4@SiO2@4-ABPT/Cu-Ni as a catalyst in the Sonogashira and C-N cross-coupling reactions in comparison with its monometallic counterparts. Additionally, the magnetic properties of the Fe3O4@SiO2@4-ABPT/Cu-Ni make it easy to separate from the reaction mixture, and it can be reused several times without a significant loss in its catalytic activity or performance.

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“…[7] Both meso-meso β-β doubly and meso-meso, β-β, β'-β' triply linked diporphyrins can extend the conjugation and cause significantly red-shifted absorption. [8][9][10][11] Therefore, they are considered promising for molecular electronics, nonlinear optics, and solar energy conversion.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Quinone Compounds Derived from Doubly and Triply Linked Diporphyrins and Tuning of Their Absorption Properties**

Yamashita,

Hirano,

Sugiura

2023

Chemistry A European J

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Porphyrins are attracting increasing attention in materials science and photochemistry owing to their unique properties and diverse applications. This study focuses on modifying and tuning the absorption properties of porphyrins, specifically those of quinoidal porphyrins, to extend their spectral range into the near‐infrared (NIR) region. We report the synthesis and structural and physical properties of quinone compounds derived from doubly and triply linked diporphyrins and their metal complexes. Doubly linked diporphyrinquinone exhibits broad panchromatic absorption properties in solution owing to its low symmetry. Metal complexation markedly extends its absorption range into the near‐infrared region. In contrast, the metal complexes of the triply linked diporphyrinquinones exhibit sharp and strong absorption bands in the visible to near‐infrared region owing to their higher symmetry. The longest absorption wavelength of the triply linked diporphyrinquinones was approximately 1500 nm, which was significantly more red‐shifted than that of the doubly linked ones.

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Metal Complexes of Singly, Doubly and Triply Linked Porphyrins and Corroles: An Insight into the Physicochemical Properties

Cited by 15 publications

References 140 publications

Electronic Coupling and Electrocatalysis in Redox Active Fused Iron Corroles

Electronic Coupling and Electrocatalysis in Redox Active Fused Iron Corroles

Conjugated Cu-Ni bimetallic complex supported on Fe 3 O 4 @SiO 2 : An efficient nanocatalyst with synergistic performance for the solvent-free Sonogashira, and C-N cross-couplings

Synthesis and Characterization of Quinone Compounds Derived from Doubly and Triply Linked Diporphyrins and Tuning of Their Absorption Properties**

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