A series of heterospin complexes based on lanthanides and pyridine biradicals: synthesis, structure and magnetic properties

Zhou, Shang Yong; Li, Xin; Li, Ting; Tian, Li; Liu, Zhong Yi; Wang, Xiu Guang

doi:10.1039/c4ra15074k

Cited by 26 publications

(10 citation statements)

References 82 publications

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“…Similarly for Dy( 4 ), M reaches 6.63 Nβ at 70 kOe, which also does not reach the saturation values of 12 Nβ (10 Nβ for one Dy(III) for J = 15/2 and g = 4/3, plus 2 Nβ for two radicals). Similar results were reported previously , which can be attributed to the magnetic anisotropy and presence of low‐lying excited states from Ln(III) ion.…”

Section: Resultssupporting

confidence: 91%

Synthesis, Crystal Structure, and Magnetic Property of New Trispin Ln(III)‐Nitronyl Nitroxide Complexes

Fan

Hou

Wang

et al. 2016

Helvetica Chimica Acta

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Four Ln(III) complexes based on a new nitronyl nitroxide radical have been synthesized and structurally characterized: {Ln(hfac)3[NITPh(MeO)2]2} (Ln = Eu(1), Gd(2), Tb(3), Dy(4); NITPh(MeO)2 = 2‐(3′,4′‐dimethoxyphenyl)‐4,4,5,5‐tetramethylimidazoline‐1‐oxyl‐3‐oxide; hfac = hexafluoroacetylacetonate). The single‐crystal X‐ray diffraction analysis shows that these complexes have similar mononuclear trispin structures, in which central Ln(III) ion is eight‐coordinated by two O‐atoms from two nitroxide groups and six O‐atoms from three hfac anions. The variable temperature magnetic susceptibility study reveals that there exist ferromagnetic interactions between Gd(III) and the radicals, and antiferromagnetic interactions between two radicals (JGd‐Rad = 3.40 cm−1, JRad‐Rad = −9.99 cm−1) in complex 2. Meanwhile, antiferromagnetic interactions are estimated between Eu(III) (or Dy(III)) and radicals in complexes 1 and 4, and ferromagnetic interaction between Tb(III) and radicals in complex 3, respectively.

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Section: Resultssupporting

confidence: 91%

Synthesis, Crystal Structure, and Magnetic Property of New Trispin Ln(III)‐Nitronyl Nitroxide Complexes

Fan

Hou

Wang

et al. 2016

Helvetica Chimica Acta

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“…[174] Compounds containing nitronyl nitroxides were first described in 1968 by Osiecki et al,a nd subsequently investigated electrochemically in detail and used in several magnetic applications. [175][176][177][178][179][180][181][182][183] PTIO,a sanovel charge-storage material for RFBs, features ap otential high solubility of about 2.6 m in acetonitrile.However, aflow cell with aPTIO concentration > 0.5 m has not been realized so far.Furthermore,acrossover of the redox-active material through the separator, which limits the CE, and ahigh viscosity of the electrolyte was observed. The state of charge and the concentration of PTIO was monitored by FTIR spectroscopy.The cycling performance of aflow cell that utilized aDaramic porous separator and 0.5 m PTIO with 1m TBAPF 6 /acetonitrile as the supporting electrolyte was investigated.…”

Section: Symmetric Redox-flow Batteries With Bipolar Organicmentioning

confidence: 99%

“…Compounds containing nitronyl nitroxides were first described in 1968 by Osiecki et al., and subsequently investigated electrochemically in detail and used in several magnetic applications …”

Section: Rise Of the Organic Active Materialsmentioning

confidence: 99%

Redox‐Flow Batteries: From Metals to Organic Redox‐Active Materials

et al. 2016

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Research on redox‐flow batteries (RFBs) is currently experiencing a significant upturn, stimulated by the growing need to store increasing quantities of sustainably generated electrical energy. RFBs are promising candidates for the creation of smart grids, particularly when combined with photovoltaics and wind farms. To achieve the goal of “green”, safe, and cost‐efficient energy storage, research has shifted from metal‐based materials to organic active materials in recent years. This Review presents an overview of various flow‐battery systems. Relevant studies concerning their history are discussed as well as their development over the last few years from the classical inorganic, to organic/inorganic, to RFBs with organic redox‐active cathode and anode materials. Available technologies are analyzed in terms of their technical, economic, and environmental aspects; the advantages and limitations of these systems are also discussed. Further technological challenges and prospective research possibilities are highlighted.

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“…1,14,35,37,38 The redox-active unit for our approach is the well-known NN radical, which was first described by Osiecki et al 39 The electrochemical behavior of NN radicals and diradicals has been investigated in detail. [40][41][42][43][44] NNs have been used as organic magnetic materials 45 and ligands for single-chain magnets 46 or single-molecule magnets; 47 furthermore, they have been used as organic memory elements 41 and the charge-storage material in an RFB application due to their n-and p-type properties. 36 In addition, NN-containing polymers are used as bipolar active electrode materials in all-organic radical batteries.…”

Section: Introductionmentioning

confidence: 99%

A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery

et al. 2017

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An all-organic symmetric redox-flow battery (RFB) that employs nitronyl nitroxide (NN) units as a bipolar redox-active chargestorage material was designed and investigated. An organic molecule possessing two bipolar redox-active NN units connected via a tetraethylene glycol chain was synthesized for this purpose. Owing to the ethylene glycol chain, this molecule demonstrates good solubility in organic solvents. The electrochemical behavior of the obtained compound was investigated via cyclic voltammetry (CV) measurements and it features quasi-reversible redox reactions of the NN + /NN redox couple at E ½ = 0.37 V and the NN/NN − redox couple at E ½ = − 1.25 V versus AgNO 3 /Ag, which led to a promising cell voltage of 1.62 V in a subsequent battery application. A static solution-based battery exhibits a stable charge/discharge performance over 75 consecutive cycles with a high energy efficiency of 82% and an overall energy density of the electrolyte system of 0.67 W h l − 1 . In addition, a pumped RFB test demonstrates an overall energy density of the electrolyte system of 4.1 W h l − 1 and an energy efficiency of 79%.

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A series of heterospin complexes based on lanthanides and pyridine biradicals: synthesis, structure and magnetic properties

Abstract: Six LnIII-biradical tri-spin complexes have been synthesized, and they exhibit interesting magnetic properties.

Cited by 26 publications

References 82 publications

Synthesis, Crystal Structure, and Magnetic Property of New Trispin Ln(III)‐Nitronyl Nitroxide Complexes

Synthesis, Crystal Structure, and Magnetic Property of New Trispin Ln(III)‐Nitronyl Nitroxide Complexes

Redox‐Flow Batteries: From Metals to Organic Redox‐Active Materials

A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery

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