Tuning the dynamic magnetic behaviour and proton conductivity <i>via</i> water-induced reversible single-crystal to single-crystal structural transformation

Ji, Xiaoqin; Sun, Rong; Xiong, Jin; Sun, Hao‐Ling; Gao, Song

doi:10.1039/d1tc03920b

Cited by 21 publications

(22 citation statements)

References 103 publications

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“…Recently, several lanthanide based molecular nanomagnets have been reported for proton conduction as emerging bifunctional magnetic materials. 32–35 Herein, the supramolecular architecture showing both magnetic and electrical functions is distinct from these reported systems based on structural and synthetic viewpoints.…”

Section: Resultsmentioning

confidence: 81%

Supramolecular encapsulation of hexaaquacobalt(ii) cations in a hydrogen-bonded framework for slow magnetic relaxation and high proton conduction

et al. 2022

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Section: Resultsmentioning

confidence: 81%

Supramolecular encapsulation of hexaaquacobalt(ii) cations in a hydrogen-bonded framework for slow magnetic relaxation and high proton conduction

et al. 2022

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“…According to the literature, structural transformation in transition-metal-based CPs occurs substantially more frequently than in lanthanide-based CPs (LnCPs), particularly when ligand substitution is concerned. In addition, almost all of the reported transformations in LnCPs prompted by a substitution of the coordinating ligands are irreversible, except only in few cases; [Ln 2 (CIP) 2 (DMF) 4– x (H 2 O) x ] (H 3 CIP = 5-(4-carboxybenzylideneamino)isophthalic acid), − {[Ln(OAc) 2 (H 2 O)(OBPT)]·3H 2 O} n (HOAc = acetic acid, HOBPT = 4,6-bis(2-pyridyl)-1,3,5-triazin-2-ol), {[Gd 2 (L) 3 (DMF) 2 (H 2 O) 2 ]·(DMF) 2 ·(H 2 O) 5.5 } n (L = 5-[(anthracen-9-ylmethyl)-amino]-isophthalic acid), and [DyCl(L)(CH 3 OH)]·CH 3 CN (L = N ′-(5-fluoro-2-hydroxybenzylidene)pyrazine- N -oxide-carbohydrazide) . In addition to ligand substitution, the thermally triggered transformation, which is reversible, is also extremely rare in LnCPs.…”

Section: Introductionmentioning

confidence: 99%

Reversible Structural Transformation and Catalytic Potential of Lanthanide-Azobenzenetetracarboxylates

2022

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Inspired by the catalytic potential of lanthanide coordination polymers of 3,3′,5,5′-azobenzenetetracarboxylic acid (H4abtc), two new isostructural [Ln2 III(Habtc)2(DMSO)4]·DMSO·H2O (LnIII = SmIII (I), EuIII = (II), DMSO = dimethyl sulfoxide) were synthesized and characterized. Their single-crystal structures were elucidated and described. Structural transformations of II in the solid state prompted by ligand substitution and thermal treatment were studied, from which genuine reversible transformation of II to [EuIII(Habtc)(H2O)4]·3H2O (II′) and [EuIII(Habtc)(H2O)2]·2H2O (II″) was revealed. This illustrates the rare case of reversible transformation in lanthanide coordination polymers. The transformation between II′ and II″ was also investigated. Structural transformations among these frameworks are discussed with regard to the coordination environment of EuIII, coordination modes of Habtc3–, and similarities and disparities in framework architecture and registration. In addition, the catalytic performance of II with and without the prior activation in CO2 cycloaddition reaction with epichlorohydrin was studied in comparison with II′ and II″. The excellent performance of II disregarding the activation process has been demonstrated with the maximum turnover number and turnover frequency of 7682 and 1921 h–1, respectively, for the activated II and 7142 and 1786 h–1, respectively, for the nonactivated II. The maintenance of the catalytic efficiency over 10 cycles of the catalysis and the regeneration process is illustrated and discussed with respect to structural transformation.

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“…Proton‐conductive magnetic compounds have been studied for years and led to a lot of fascinating multifunctional materials, including proton‐conductive magnetic ordering materials [20–25] . Interestingly, some single‐molecule magnets (SMMs) are emerging as new bifunctional magnetic materials with proton conduction [26–29] . Yet proton conductive SCO material has not yet been reported.…”

Section: Introductionmentioning

confidence: 99%

A Proton Conducting Cobalt(II) Spin Crossover Complex

Shao

Yang

Wei

et al. 2022

Chemistry An Asian Journal

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Spin crossover (SCO) complexes have been extensively explored as bistable materials and recently used as molecular modules for the development of new multifunctional molecular magnetic materials. Herein, we present the synthesis, crystal structure, magnetic, and electrical properties of a mononuclear cobalt complex constructed by a halogenfunctionalized terpyridine derivative and organosulfonate. A complete and gradual spin transition with the T 1/2 = 200 K was observed for the Co 2 + ions through both the magnetic measurement and dynamic crystallographic experiments.Interestingly, considerable room temperature proton conductivity of 6.9 × 10 À 5 S cm À 1 under 98% relative humidity was evidenced because of the presence of sulfonate-assisted hydrogen-bonded proton hopping pathways. The forgoing results not only provide an unprecedented proton-conducting cobalt(II) SCO complex but also a promising way for the design and construction of bifunctional SCO molecular conductors via the incorporation of SCO transition and proton conduction.

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Tuning the dynamic magnetic behaviour and proton conductivity via water-induced reversible single-crystal to single-crystal structural transformation

Abstract: Employing external stimuli to manipulate the synergy between magnetic and proton conductivity has stimulated extensive scientific interest due to the potential application in information storage, sensors and fuel cell, etc....

Cited by 21 publications

References 103 publications

Supramolecular encapsulation of hexaaquacobalt(ii) cations in a hydrogen-bonded framework for slow magnetic relaxation and high proton conduction

Supramolecular encapsulation of hexaaquacobalt(ii) cations in a hydrogen-bonded framework for slow magnetic relaxation and high proton conduction

Reversible Structural Transformation and Catalytic Potential of Lanthanide-Azobenzenetetracarboxylates

A Proton Conducting Cobalt(II) Spin Crossover Complex

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