A spin crossover (SCO) active graphene-iron(<scp>ii</scp>) complex hybrid material

Kumar, Kuppusamy Senthil; Šalitroš, Ivan; Boubegtiten-Fezoua, Zahia; Moldovan, Simona; Hellwig, Petra; Rüben, Mario

doi:10.1039/c7dt03623j

Cited by 24 publications

(10 citation statements)

References 63 publications

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“…In this context, emerging graphene-based SCO composites will likely play also an important role, exploiting couplings to the unique electrical, mechanical and thermal properties of graphene. [134][135][136] -Whereas reports on SCO-polymer composites and 'soft SCO materials' functionalized with alkyl chains are numerous, less attention have been devoted to the synthesis of "SCO-organic polymers". We believe such compounds hold important promises, in particular for biomedical and life sciences, and we expect that their development will intensify in the near future.…”

Section: Concluding Remarks and Prospectsmentioning

confidence: 99%

Spin crossover polymer composites, polymers and related soft materials

Enríquez-Cabrera

Rapakousiou

Piedrahita‐Bello

et al. 2020

Coordination Chemistry Reviews

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We review the synthesis, properties and applications of spin crossover polymer composites, polymers and some related 'soft' materials. These materials have received recently much attention because they provide an efficient way for the processing of spin crossover complexes in various shapes at various size scales and can give rise also to unique physical properties. First, we discuss in detail the state of the art of the elaboration of spin crossover polymer composites, using either inorganic complex precursors in solution or pre-formed spin crossover powder. A particular attention is paid on the influence of the polymer matrix on the spin crossover properties and on the use of 'active' polymers for development of synergies between the properties of the matrix and the load. Polymer composite devices for applications in the fields of artificial muscles, energy harvesting and thermochromic sensors are also highlighted. Then, more recent works, in which organic polymeric chains are used as ligands for the transition metal ions are presented. Finally, we overview various related 'soft' spin crossover compounds including spin crossover dendrimers, gels, liquid crystals and Langmuir Blodgett films with particular emphasis on compounds with supramolecular interactions of alkyl chains.

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Section: Concluding Remarks and Prospectsmentioning

confidence: 99%

Spin crossover polymer composites, polymers and related soft materials

Enríquez-Cabrera

Rapakousiou

Piedrahita‐Bello

et al. 2020

Coordination Chemistry Reviews

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“…By preparing a graphene−SCO complex hybrid material, we have elucidated that the interface between the molecule and graphene surface modifies the SCO parameters, relative to the parameters observed in the bulk state. 57 Subsequently, we have demonstrated spin-state dependence of conductance characteristics at a single-molecule junction composed of SLG electrodes and a pyrene-tethered iron(II)–BPP complex. 24 In another direction, we have studied transport characteristics of SCO–gold nanoparticle (Au–NP) hybrid ensembles, demonstrating the utility of iron(II)–BPP complexes featuring sulfur-based anchoring groups for the development of SCO molecule-based spintronic architectures.…”

Section: Introductionmentioning

confidence: 99%

Spin-Crossover in Supramolecular Iron(II)–2,6-bis(1H-Pyrazol-1-yl)pyridine Complexes: Toward Spin-State Switchable Single-Molecule Junctions

et al. 2022

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Spin-crossover (SCO) active iron(II) complexes are an integral class of switchable and bistable molecular materials. Spin-state switching properties of the SCO complexes have been studied in the bulk and single-molecule levels to progress toward fabricating molecule-based switching and memory elements. Supramolecular SCO complexes featuring anchoring groups for metallic electrodes, for example, gold (Au), are ideal candidates to study spin-state switching at the single-molecule level. In this study, we report on the spin-state switching characteristics of supramolecular iron(II) complexes 1 and 2 composed of functional 4-([2,2′-bithiophen]-5-ylethynyl)-2,6-di(1 H -pyrazol-1-yl)pyridine ( L1 ) and 4-(2-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)ethynyl)-2,6-di(1 H -pyrazol-1-yl)pyridine ( L2 ) ligands, respectively. Density functional theory (DFT) studies revealed stretching-induced spin-state switching in a molecular junction composed of complex 1 , taken as a representative example, and gold electrodes. Single-molecule conductance traces revealed the unfavorable orientation of the complexes in the junctions to demonstrate the spin-state dependence of the conductance.

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“…Thus, [Fe(bpp) 2 ] 2+ derivatives bearing redox-active, conducting, fluorescent, , photoisomerizable, magnetically active, or metal-binding ,, substituents have been produced, in many cases yielding dual SCO switching functionality. Alternatively, bpp ligands and complexes with suitable tether groups have been deposited onto gold or graphite surfaces or in single-molecule junctions …”

Section: Introductionmentioning

confidence: 99%

2,6-Bis(pyrazol-1-yl)pyridine-4-carboxylate Esters with Alkyl Chain Substituents and Their Iron(II) Complexes

et al. 2018

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Two series of 4-(alkoxyphenyl) 2,6-bis{pyrazol-1-yl}pyridine-4-carboxyate (L3R) or alkyl 2,6-bis{pyrazol-1-yl}pyridine-4-carboxyate (L4R) esters have been synthesized and complexed to iron(II), where R = C n H2n+1 (n = 6, 12, 14, 16, 18); two other derivatives related to L3R are also reported. While the solid [Fe(L4R)2][BF4]2 compounds are isostructural by powder diffraction and show similar spin state behaviors, the [Fe(L3R)2][BF4]2 series shows more varied structures and magnetic properties. This was confirmed by solvated crystal structures of [Fe(L3R)2][BF4]2 with n = 6, 14, 16, which all adopt the P1̅ space group but show significantly different side-chain conformations and/or crystal packing. The solid complexes are mostly low spin at room temperature, with many exhibiting the onset of thermal spin crossover (SCO) upon warming. Heating the complexes with n ≥ 14 significantly above their SCO temperature transforms them irreversibly into a predominantly high spin state, which is accompanied by structure changes and loss of crystallinity by powder diffraction. These transformations do not coincide with lattice solvent loss and may reflect melting and refreezing of their alkyl chain conformations during the thermal cycle. Four of the complexes exhibit SCO in CD3CN solution with T 1/2 = 273–277 K, which is apparently unaffected by their alkyl chain substituents.

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A spin crossover (SCO) active graphene-iron(ii) complex hybrid material

Cited by 24 publications

References 63 publications

Spin crossover polymer composites, polymers and related soft materials

Spin crossover polymer composites, polymers and related soft materials

Spin-Crossover in Supramolecular Iron(II)–2,6-bis(1H-Pyrazol-1-yl)pyridine Complexes: Toward Spin-State Switchable Single-Molecule Junctions

2,6-Bis(pyrazol-1-yl)pyridine-4-carboxylate Esters with Alkyl Chain Substituents and Their Iron(II) Complexes

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