Spectroscopic and structural investigation of oxocarbon salts with tetraalkylammonium ions

Georgopoulos, Stéfanos Leite; Garcia, Humberto C.; Edwards, Howell G. M.; Oliveira, Luiz Fernando Cappa de

doi:10.1016/j.molstruc.2015.12.049

Cited by 3 publications

(1 citation statement)

References 48 publications

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“…Its name derives from the yellow color of its metal salts, which is highly reminiscent of some variants of the crocus flower and of egg yolk. With its planar structure, its (nearly) perfect fivefold symmetry, even in the crystalline state [ 43 , 44 , 45 ], and its two delocalized π-electrons, the croconate dianion meets the formal criteria of a Hückel arene ( Figure 2 ). Quantum chemical studies however indicate that its degree of aromaticity is considerably lower than that of ordinary arenes [ 44 , 46 ].…”

Section: Introductionmentioning

confidence: 99%

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

et al. 2021

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Careful optimization of the reaction conditions provided access to the particularly small tetraruthenium macrocycle 2Ru2Ph-Croc, which is composed out of two redox-active divinylphenylene-bridged diruthenium entities {Ru}-1,4-CH=CH-C6H4-CH=CH-{Ru} (Ru2Ph; {Ru} = Ru(CO)Cl(PiPr3)2) and two likewise redox-active and potentially non-innocent croconate linkers. According to single X-ray diffraction analysis, the central cavity of 2Ru2Ph-Croc is shielded by the bulky PiPr3 ligands, which come into close contact. Cyclic voltammetry revealed two pairs of split anodic waves in the weakly ion pairing CH2Cl2/NBu4BArF24 (BArF24 = [B{C6H3(CF3)2-3,5}4]- electrolyte, while the third and fourth waves fall together in CH2Cl2 / NBu4PF6. The various oxidized forms were electrogenerated and scrutinized by IR and UV/Vis/NIR spectroscopy. This allowed us to assign the individual oxidations to the metal-organic Ru2Ph entities within 2Ru2Ph-Croc, while the croconate ligands remain largely uninvolved. The lack of specific NIR bands that could be assigned to intervalence charge transfer (IVCT) in the mono- and trications indicates that these mixed-valent species are strictly charge-localized. 2Ru2Ph-Croc is hence an exemplary case, where stepwise IR band shifts and quite sizable redox splittings between consecutive one-electron oxidations would, on first sight, point to electronic coupling, but are exclusively due to electrostatic and inductive effects. This makes 2Ru2Ph-Croc a true “pretender”.

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Section: Introductionmentioning

confidence: 99%

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

et al. 2021

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Oxocarbons Electrode Materials for Alkali Ion Batteries: Challenges, Strategies and Development

Zhang

et al. 2021

Batteries & Supercaps

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Benefiting from the high theoretic capacity, structural designability, low cost, abundant resources and sustainability, oxocarbons materials have attracted extensive attention as a promising candidate to replace inorganic electrode materials for alkali ion batteries (AIBs). This review focuses on the indepth evaluation of the electrochemical properties of oxocarbons for lithium, sodium and potassium ion batteries. Further, we summarize the evolution, challenges and opportunities of oxocarbon compounds based on our current understanding. In addition, we identified two main aspects that limit their applications as electrode materials: 1) inferior conductivity and 2) fast capacity decay. Hence, in this review we also integrate different strategies to improve these two aspects, e. g., compositing with carbon, grafting conductive polymers, nanostructuring, optimizing electrolytes, designing interface, and selecting appropriate binders. This review can be useful to understand the practical application and commercial feasibility of such materials for different AIBs applications.

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Vibrational and structural studies of new Cu2+ and Co2+ complexes based on croconate ion and 5,5’-dimethyl-2,2’-dipiridyl ligands

Souza

Ferreira²,

Flores

et al. 2020

Vibrational Spectroscopy

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Spectroscopic and structural investigation of oxocarbon salts with tetraalkylammonium ions

Cited by 3 publications

References 48 publications

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

A “Pretender” Croconate-Bridged Macrocyclic Tetraruthenium Complex: Sizable Redox Potential Splittings despite Electronically Insulated Divinylphenylene Diruthenium Entities

Oxocarbons Electrode Materials for Alkali Ion Batteries: Challenges, Strategies and Development

Vibrational and structural studies of new Cu2+ and Co2+ complexes based on croconate ion and 5,5’-dimethyl-2,2’-dipiridyl ligands

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