Metal(II) N2S2 Schiff-base complexes incorporating pyrazole or isoxazole (M = Ni, Cu or Zn). Spin states, racemization kinetics and electrochemistry

Cour, Agnete la; Findeisen, Matthias; Hazell, Alan; Hazell, Rita G.; Zdobinsky, Grit

doi:10.1039/a602281b

Cited by 12 publications

(6 citation statements)

References 24 publications

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“…The cyclic voltammogram of Ni‐TFT (0.1 m m ), recorded in DMF solution, display two reduction waves related to the Ni II /Ni I and Ni I /Ni 0 reduction process around −1.2–1.5 V(vs. Ag/AgCl), respectively. These potentials fall well in the range for proton reduction in aqueous media . Indeed, the addition of Et 3 NH + (Et 3 N, triethylamine) to the Ni‐TFT solution (DMF) leads to a new wave near the redox peak at −1.50 V that increases with increasing acid concentration (Figure a), indicating that Ni‐TFT acts as an electro‐catalyst for proton reduction.…”

Section: Methodsmentioning

confidence: 85%

Control of Redox Events by Dye Encapsulation Applied to Light‐Driven Splitting of Hydrogen Sulfide

Yang

et al. 2017

Angew Chem Int Ed

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Solar production of hydrogen by consuming low-value waste products is an attractive pathway that has both economic and environmental benefits. Inspired by the reactive pocket of enzymes, a synthetic platform to combine photocatalytic hydrogen evolution with sulfide oxidation in a one-pot process via control over the location of the electron-transfer steps is developed. The redox-active coordination vessel Ni-TFT, which has an octahedral pocket, encapsulates an organic dye to pre-organize for photocatalytic proton reduction via an oxidative quenching pathway using the nickel corners as catalysts, generating molecular hydrogen and the oxidized dye. The oxidized dye is displaced by a neutral dye and oxidizes sulfide once outside the pocket to give element sulfur. The overall reaction constitutes hydrogen sulfide splitting, forming molecular hydrogen and elemental sulfur, which is analogous to the water-splitting reaction.

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Section: Methodsmentioning

confidence: 85%

Control of Redox Events by Dye Encapsulation Applied to Light‐Driven Splitting of Hydrogen Sulfide

Yang

et al. 2017

Angew Chem Int Ed

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“…The delocalization of the π system in the cyclopentene fragment indicates that this co-ordinates in a Schiff-base mode, in accordance with the similarity of the two Ni᎐N bond lengths and the Ni᎐S bond length that is typical of anionic sulfur donors in low-spin nickel() complexes. [4][5][6] This kind of coordination mode was observed for several complexes containing related ligands, 3,7,8 and contrasts with the behaviour of the free proligand, for which the dithioester/amine form is predominant. 9, 10 The structure of complex 1 may be compared to those containing the symmetric ligands salpd and cd 2 pd.…”

Section: Crystal Structure Of [Ni(cdsalpd)]mentioning

confidence: 79%

Synthesis, spectroscopic and electrochemical study of nickel-(II) and -(I) complexes with Schiff-base ligands giving a NN′OS co-ordination sphere

Pereira¹,

Gomes²,

Castro³

1998

J. Chem. Soc., Dalton Trans.

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“…C24 bears tritopic triphenylamine ligands 28 with hydrazinecarbothioamide coordinating moieties, which are self-assembled in situ during cage formation. The photosensitizer fluorescein 15 can bind in the cavity, once more preassembling both PS and the catalytic center . Photochemical H 2 evolution was performed using TEA as a sacrificial electron donor in a H 2 O:EtOH (1:1) mixture at pH = 12.6, obtaining an initial TOF of 1250 mol of hydrogen per mole of catalyst per hour and a TON of 25000 per mole of C24 .…”

Section: Coordination Cages For Artificial Photosynthesismentioning

confidence: 99%

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

et al. 2023

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Because sunlight is the most abundant energy source on earth, it has huge potential for practical applications ranging from sustainable energy supply to light driven chemistry. From a chemical perspective, excited states generated by light make thermodynamically uphill reactions possible, which forms the basis for energy storage into fuels. In addition, with light, open-shell species can be generated which open up new reaction pathways in organic synthesis. Crucial are photosensitizers, which absorb light and transfer energy to substrates by various mechanisms, processes that highly depend on the distance between the molecules involved. Supramolecular coordination cages are well studied and synthetically accessible reaction vessels with single cavities for guest binding, ensuring close proximity of different components. Due to high modularity of their size, shape, and the nature of metal centers and ligands, cages are ideal platforms to exploit preorganization in photocatalysis. Herein we focus on the application of supramolecular cages for photocatalysis in artificial photosynthesis and in organic photo(redox) catalysis. Finally, a brief overview of immobilization strategies for supramolecular cages provides tools for implementing cages into devices. This review provides inspiration for future design of photocatalytic supramolecular host−guest systems and their application in producing solar fuels and complex organic molecules.

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Metal(II) N2S2 Schiff-base complexes incorporating pyrazole or isoxazole (M = Ni, Cu or Zn). Spin states, racemization kinetics and electrochemistry

Cited by 12 publications

References 24 publications

Control of Redox Events by Dye Encapsulation Applied to Light‐Driven Splitting of Hydrogen Sulfide

Control of Redox Events by Dye Encapsulation Applied to Light‐Driven Splitting of Hydrogen Sulfide

Synthesis, spectroscopic and electrochemical study of nickel-(II) and -(I) complexes with Schiff-base ligands giving a NN′OS co-ordination sphere

Supramolecular Coordination Cages for Artificial Photosynthesis and Synthetic Photocatalysis

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