From Tetranuclearµ4-Oxo toµ4-Peroxocopper(II) Complexes

Reim, Jörg; Werner, Rüdiger; Haase, Wolfgang; Krebs, Bernt

doi:10.1002/(sici)1521-3765(19980210)4:2<289::aid-chem289>3.0.co;2-2

Cited by 66 publications

(16 citation statements)

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“…The spectra of both complexes exhibited strong absorption bands at around 380 and 672 nm ( ε ≈18 000 and 300 M −1 cm −1 , respectively). The higher energy band is assigned to a pπ phenolate →dπ* copper charge‐transfer band, whereas the lower energy band is attributed to a d–d transition of the metal,30, 33–35 probably b 3g →b 1g in nature, reflecting an idealized local symmetry C 4 v expected for each of the square pyramidal copper(II) ions. A weak shoulder at about 800 nm can represent a deviation from this idealized C 4 v environment either due to the presence of distinct donor sets or due to a square‐planar character.…”

Section: Resultsmentioning

confidence: 99%

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L₂Cu₄(μ₄‐O)(μ₂‐carboxylato)₄] Soft Materials

Shakya¹,

Hindo²,

Wu³

et al. 2007

Chemistry A European J

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A general approach toward amphiphilic systems bearing multimetallic clusters and their ability to form Langmuir-Blodgett films is presented. The synthetic strategy to stabilize these clusters involves the use of a ligand (HL) containing an N(2)O-donor set and long octadecanoic chains to obtain the carboxylate-supported [L(2)Cu(4)(mu(4)-O)(mu(2)-OAc)(4)]EtOH (1) and [L(2)Cu(4)(mu(4)-O)(mu(2)-OBz)(4)] (2) in which OAc(-) and OBz(-) represent acetate (1) and benzoate (2) co-ligands. These species were thoroughly characterized and had their structures solved by X-ray crystallography. We observed that the mu-oxo Cu(4) cluster is antiferromagnetically coupled and used broken-symmetry density functional theory (DFT) calculations to describe the main superexchange pathways of the tetracopper core. We also describe the amphiphilic properties of the ligand and the cluster-containing systems by means of area versus pressure isotherms and show that these cluster-bearing species can be transferred onto solid substrates yielding homogeneous Langmuir-Blodgett films, as characterized by atomic force microscopy and contact angle measurements.

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Section: Resultsmentioning

confidence: 99%

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L₂Cu₄(μ₄‐O)(μ₂‐carboxylato)₄] Soft Materials

Shakya¹,

Hindo²,

Wu³

et al. 2007

Chemistry A European J

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“…could be concluded . To confirm the formation of μ 4 ‐coordinated peroxide in situ, we added H 2 O 2 to chemically generate μ 4 ‐coordinated peroxide . The same peak position at 875 cm −1 of the in situ generated and chemically generated species in their Raman spectra (Supporting Information, Figure S18) manifested the

\overset{ν}{true}

(O−O) of the μ 4 ‐coordinated peroxide .…”

Section: Figurementioning

confidence: 88%

A Bio‐inspired Cu₄O₄ Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Jiang

Yang

et al. 2018

Angew Chem Int Ed

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Inspired by the cubic Mn CaO cluster of natural oxygen-evolving complex in Photosystem II, tetrametallic molecular water oxidation catalysts, especially M O cubane-like clusters (M=transition metals), have aroused great interest in developing highly active and robust catalysts for water oxidation. Among these M O clusters, however, copper-based molecular catalysts are poorly understood. Now, bio-inspired Cu O cubanes are presented as effective molecular catalysts for electrocatalytic water oxidation in aqueous solution (pH 12). The exceptional catalytic activity is manifested with a turnover frequency (TOF) of 267 s for [(L -Cu) ] at 1.70 V and 105 s for [(L -Cu) ] at 1.56 V. Electrochemical and spectroscopic study revealed a successive two-electron transfer process in the Cu O cubanes to form high-valent Cu and Cu O intermediates during the catalysis.

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“…168 The full structural description and accompanying discussion of the |X 4 -peroxo complex described by Krebs and co-workers has been published. 169 Utilizing molecular modeling (i.e. molecular mechanics) design aids, Comba and co-workers have synthesized and characterized new end-on u.-peroxo-dicopper (i.e.…”

Section: Note Added In Proofmentioning

confidence: 99%

Models of Copper Enzymes and Heme-Copper Oxidases

Kopf¹,

Karlin²

2000

Biomimetic Oxidations Catalyzed by Transition Metal Complexes

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From Tetranuclearµ4-Oxo toµ4-Peroxocopper(II) Complexes

Cited by 66 publications

References 0 publications

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L₂Cu₄(μ₄‐O)(μ₂‐carboxylato)₄] Soft Materials

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L₂Cu₄(μ₄‐O)(μ₂‐carboxylato)₄] Soft Materials

A Bio‐inspired Cu₄O₄ Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Models of Copper Enzymes and Heme-Copper Oxidases

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From Tetranuclearµ4-Oxo toµ4-Peroxocopper(II) Complexes

Cited by 66 publications

References 0 publications

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L2Cu4(μ4‐O)(μ2‐carboxylato)4] Soft Materials

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L2Cu4(μ4‐O)(μ2‐carboxylato)4] Soft Materials

A Bio‐inspired Cu4O4 Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Models of Copper Enzymes and Heme-Copper Oxidases

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Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L₂Cu₄(μ₄‐O)(μ₂‐carboxylato)₄] Soft Materials

Amphiphilic and Magnetic Properties of a New Class of Cluster‐Bearing [L₂Cu₄(μ₄‐O)(μ₂‐carboxylato)₄] Soft Materials

A Bio‐inspired Cu₄O₄ Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution