Immobilization of functionalized iron(II) clathrochelates with terminal (poly)aromatic group(s) on carbonaceous materials and their detailed cyclic voltammetry study

Voloshin, Yan Z.; Chornenka, Nina V.; Varzatskii, Оleg А.; Belov, Alexander S.; Grigoriev, S.A.; Pushkarev, Artem S.; Millet, Pierre; Kalinichenko, Valery N.; Belaya, Irina; Bugaenko, M. G.; Дедов, А. Г.

doi:10.1016/j.electacta.2018.03.030

Cited by 11 publications

(11 citation statements)

References 9 publications

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“…There is hence a simple correlation between the number of polyaromatic groups per a clathrochelate molecule (from one to six) and the strength of adsorption. A similar trend was reported earlier [7] while using RGO used as carbonaceous substrate.…”

Section: Study Of the Physisorption Of Iron(ii) Clathrochelatessupporting

confidence: 89%

“…Three different complexes of interest, namely FeBd 2 ((Phen(CH 2 ) 3 S)GmH)(BF) 2 , FeBd 2 ((Phen(CH 2 ) 3 S) 2 Gm)(BF) 2 (where Bd 2stands for α-benzildioxime dianion and Gm stands for glyoxime residue) and Fe((Phen(CH 2 ) 3 S) 2 Gm) 3 (Bn-C 4 H 9 ) 2 , were prepared as described elsewhere. [6,7] Carbon paper (CP) Sigracet GDL 39 BC (SGL Group) was used in adsorption experiments.…”

Section: Methodsmentioning

confidence: 99%

“…Several results have been reported in a previous publication. [7] Carbon paper with its very large surface area is known as a material of practical interest in the electrochemical industry. It can be used as gas-diffusion-layer (GDL) in PEM fuel cell technology and as cathode current collector in PEM water electrolysis technology.…”

Section: Introductionmentioning

confidence: 99%

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Spectrophotometrical Study of the Physisorption of Iron(II) Clathrochelates Containing Terminal Phenanthrenyl Group(s) on Carbon Paper

Voloshin¹,

Chornenka²,

Belov³

et al. 2018

MHC

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Transition metal clathrochelates form a family of the compounds of great practical interest for the hydrogen evolution reaction in acidic electrolytes. When adequately immobilized on the surface of appropriate carbonaceous substrates, they can find application at the cathode of polymer electrolyte membrane water electrolysis cells. The physisorption of the mono-, di-and hexa-functionalized phenanthrenyl-terminated iron(II) clathrochelates, which were especially designed for their effective immobilization onto carbonaceous substrates, onto a carbon paper of practical interest, was studied by UV-Vis spectrophotometry. It was found that the larger the number of polyaromatic groups per a clathrochelate molecule, the stronger the physisorption is. Despite a larger steric hindrance, the complexes with several polyaromatric groups are prone to stronger physisorption on carbonaceous substrates. The physisorption of Methylene Blue dye, a model compound, was used as reference for comparison.

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Section: Study Of the Physisorption Of Iron(ii) Clathrochelatessupporting

confidence: 89%

Section: Methodsmentioning

confidence: 99%

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Spectrophotometrical Study of the Physisorption of Iron(II) Clathrochelates Containing Terminal Phenanthrenyl Group(s) on Carbon Paper

Voloshin¹,

Chornenka²,

Belov³

et al. 2018

MHC

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“…An original method of using graphene as a support of molecular electrocatalysts for hydrogen evolution was demonstrated in the studies of Russian researchers, including those performed at the National Research Center Kurchatov Institute [ 126 ]. The clathrochelate complexes of Fe, Co, and Ru can be adsorbed on the developed RGO surface, which makes it possible to significantly increase the efficiency and productivity of the cathode of a PEM water electrolyzer [ 127 , 128 ]. A similar approach can be used in the case of molecular electrocatalysts of the ORR, etc.…”

Section: Application Of Graphene In Electrocatalytic Layers Of Polmentioning

confidence: 99%

Graphene and Graphene-Like Materials for Hydrogen Energy

et al. 2020

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The review is devoted to current and promising areas of application of graphene and materials based on it for generating environmentally friendly hydrogen energy. Analysis of the results of theoretical and experimental studies of hydrogen accumulation in graphene materials confirms the possibility of creating on their basis systems for reversible hydrogen storage, which combine high capacity, stability, and the possibility of rapid hydrogen evolution under conditions acceptable for practical use. Recent advances in the development of chemically and heat-resistant graphene-based membrane materials make it possible to create new gas separation membranes that provide high permeability and selectivity and are promising for hydrogen purification in processes of its production from natural gas. The characteristics of polymer membranes that are currently used in industry for the most part can be significantly improved with small additions of graphene materials. The use of graphene-like materials as a support of nanoparticles or as functional additives in the composition of the electrocatalytic layer in polymer electrolyte membrane fuel cells makes it possible to improve their characteristics and to increase the activity and stability of the electrocatalyst in the reaction of oxygen evolution.

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“…Most often, an SCO is encountered in (pseudo)octahedral complexes of iron(II) in a N6-coordination environment, , such as provided by many bi- − and tridentate − N-donor heterocyclic ligands or ligands of higher denticity. − From the latter group, a unique class of extended-tripodal (cage) ligands produces rigid and chemically stable transition-metal complexes, so-called clathrochelates, which can be easily synthesized by self-assembly on an appropriate metal ion, functionalized at several (apical and ribbed) positions by various functional groups , and applied onto surfaces via chemical bonding or deposition from solutions, all being important qualities for practical applications in molecular sensing, electronics, and spintronics . The HS cobalt(II) clathrochelates (or pseudoclathrochelates if one capping boron atom is missing; Scheme ) often show a single-molecule magnet (SMM) behavior with some record values for cobalt(II) compounds, , and in rare cases, , they undergo a temperature-induced SCO, sometimes anticooperative, stemming from a trigonal-prismatic geometry imposed by the rigid cage ligand and its resistance to distortions .…”

Section: Introductionmentioning

confidence: 99%

First Iron(II) Clathrochelate with a Temperature-Induced Spin Crossover to an Elusive High-Spin State

Denisov

Novikov

Belova

et al. 2021

Crystal Growth & Design

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Here, we report the first (pseudo)clathrochelate of iron(II) to undergo a temperature-induced spin crossover (SCO) to an elusive high-spin state “trapped” in one of its solvatomorphs. An SCO-inducing ability of the resulting extended-tripodal (cage) ligand in an otherwise SCO-inactive type of iron(II) complexes arises from its molecular design that adapts to the metal ion in the two spin states by experiencing a massive trigonal twist distortion. Combined with the amenability of this ligand to further functionalization to produce a series of iron(II) (pseudo)clathrochelates with tunable SCO behaviors, it opens up a possibility for this unique class of trigonal-prismatic complexes to soon emerge as effective switchable components for molecular electronics and spintronics.

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Immobilization of functionalized iron(II) clathrochelates with terminal (poly)aromatic group(s) on carbonaceous materials and their detailed cyclic voltammetry study

Cited by 11 publications

References 9 publications

Spectrophotometrical Study of the Physisorption of Iron(II) Clathrochelates Containing Terminal Phenanthrenyl Group(s) on Carbon Paper

Spectrophotometrical Study of the Physisorption of Iron(II) Clathrochelates Containing Terminal Phenanthrenyl Group(s) on Carbon Paper

Graphene and Graphene-Like Materials for Hydrogen Energy

First Iron(II) Clathrochelate with a Temperature-Induced Spin Crossover to an Elusive High-Spin State

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