Cyclic voltammetry of iron dimine complexes in acetonitrile

Chum, Helena L.; Rock, Monica; Murakami, Neyde Y.; Jordan, I; Rabockai, T.

doi:10.1016/s0022-0728(77)80480-4

Cited by 19 publications

(8 citation statements)

References 17 publications

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“…Complex 17 shows also a quasi‐reversible process [iron(II)/iron(III)] at 0.72 V (reduction potential) and 0.83 V (oxidation potential), in good agreement with the values reported in literature (1.07 V vs. Ag/AgCl in 0.2 m NEt 4 ClO 4 /MeCN). Please note the strong impact of the used chelate ligand on the redox potentials.…”

Section: Resultssupporting

confidence: 90%

Iron(II) and Iron(III) Complexes of Tridentate NNO Schiff Base‐like Ligands – X‐ray Structures and Magnetic Properties

Dankhoff

Schneider

Nowak

et al. 2018

Zeitschrift anorg allge chemie

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A series of new [Fe(L)2] iron(II) and [Fe(L)2]X iron(III) complexes is presented with varying tridentate NNO coordinating Schiff base‐like ligands (L–) and different counterions (X– = Cl–, Br–, I– BF4–, PF6–, and ClO4–) in the case of the iron(III) complexes. The crystal structures of one iron(II) and three iron(III) complexes are discussed, as well as the magnetic properties of the complexes regarding the possibility of the observation of spin crossover. While the three iron(II) complexes are predominantly high spin, in the case of the iron(III) complexes spin crossover was observed for the majority of the complexes (10 out of 12). Additionally, the optical properties and electrochemical behavior in solution was investigated and the results are compared with related systems from literature.

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Section: Resultssupporting

confidence: 90%

Iron(II) and Iron(III) Complexes of Tridentate NNO Schiff Base‐like Ligands – X‐ray Structures and Magnetic Properties

Dankhoff

Schneider

Nowak

et al. 2018

Zeitschrift anorg allge chemie

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“…Indeed, these values are expected to be smaller when taking into the account the experimental boundaries of the EW of MeCN (i. e., 3.59 and 3.68 V) or MeCN doped with ionic liquids (i. e., 5.09 and 6.14 V), but still significantly larger than those of all existing commercially employed aqueous RFBs. By comparing these values with previously reported non‐aqueous systems it is evident that they are higher than those that are promising for the use in RFBs, such as M‐acacs: 1.75 V in Ru(acac) 3 , [111] 2.20 V in V(acac) 3 , [68] 3.40 V in Cr(acac) 3 , [112] or pyridyl‐containing complexes within the +3⇄−1 range, previously reported for these systems: 2.71 V Fe(bpy) 3 [113] and 3.14 V in Fe(tpy) 2 [114] . It should be noted that while these two designed complexes do exhibit multiple redox events and high OCV values, before they are employed as charge carriers in commercial RFBs, further studies of compound solubility, transport kinetics across the charge states, reversibility, and other parameters should also be considered.…”

Section: Computational Efforts To Improve Performance Of Rfbsmentioning

confidence: 84%

A Comparative Review of Metal‐Based Charge Carriers in Nonaqueous Flow Batteries

et al. 2020

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Energy storage is becoming the chief barrier to the utilization of more renewable energy sources on the grid. With independent service operators aiming to acquire gigawatts in the next 10–20 years, there is a large need to develop a suite of new storage technologies. Redox flow batteries (RFB) may be part of the solution if certain key barriers are overcome. This Review focuses on a particular kind of RFB based on nonaqueous media that promises to meet the challenge through higher voltages than the organic and aqueous variants. This class of RFB is divided into three groups: molecular, macromolecular, and redox‐targeted systems. The growing field of theoretical modeling is also reviewed and discussed.

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“…Since complex II has two pyridyl moieties, one should compare it to the previously reported redox potentials of the M(bpy) 3 and M(tpy) 2 complexes (M=Fe, Ru) (vs. Fc 0 /Fc + ) in the +3 → −1 charge states [76]. Within this range, the OCV value of complex II (4.74 V) is also higher than those of Fe(bpy) 3 (2.71 V [77,78] and 2.80 V [76]), Ru(bpy) 3 (2.88 V) [79,80], Fe(tpy) 2 (3.14 V) [76], and Ru(tpy) 2 (3.24 V) [81][82][83]. Indeed, the expansion of the EW by ILs could further increase the OCV values of all complexes.…”

Section: Reduction Potentialsmentioning

confidence: 87%

Catalyst-Inspired Charge Carriers for High Energy Density Redox Flow Batteries

et al. 2019

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We introduce a theoretical design approach aiming at improving energy density of redox flow batteries (RFBs) via the utilization of redox non-innocent ligands capable of stabilizing a metal center in a wide range of oxidation states. Our findings suggest that this promotes the possibility of multiple redox events as well as high open circuit voltages. Specifically, we have proposed two Fe-coordination complexes (I, Fe(Me2 Pytacn)(C 2 N 3 H 2), and II, Fe(H 2 pmen)(C 2 N 3 H 2)) combining two different types of ligands, i.e., catalyst-inspired scaffolds and triazole ring, which were previously shown to promote high and low oxidation states in transition metals, respectively. These complexes exhibit as many as six theoretical redox events in the full range of charge states +4 → −2, several of which reside within the electrochemical window of acetonitrile. Electronic structure calculations show that the Fe center exhibits oxidation states ranging from the very rare Fe 4+ to Fe 1+. Values of the reduction potentials as well as nature of the redox events of both complexes is found to be similar in their high +4 → +1 charge states. In contrast, while exhibiting qualitatively similar redox behavior in the lower 0 → −2 range, some differences in the electronic ground states, delocalization patterns as well as reduction potential values are also observed. The calculated open circuit voltages can reach values of 5.09 and 6.14 V for complexes I and II, respectively, and hold promise to be experimentally accessible within the electrochemical window of acetonitrile expanded by addition of ionic liquids. The current results obtained for these two complexes are intended to illustrate a more general principle based on the simultaneous utilization of two types of ligands responsible for the stabilization of high and low oxidation states of the metal that can be used to design the next-generation charge carriers capable of supporting multi-electron redox and operating in a broad range of charge states, leading to RFBs with greater energy density.

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Cyclic voltammetry of iron dimine complexes in acetonitrile

Cited by 19 publications

References 17 publications

Iron(II) and Iron(III) Complexes of Tridentate NNO Schiff Base‐like Ligands – X‐ray Structures and Magnetic Properties

Iron(II) and Iron(III) Complexes of Tridentate NNO Schiff Base‐like Ligands – X‐ray Structures and Magnetic Properties

A Comparative Review of Metal‐Based Charge Carriers in Nonaqueous Flow Batteries

Catalyst-Inspired Charge Carriers for High Energy Density Redox Flow Batteries

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