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Spin crossover polymer composites, polymers and related soft materials

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In this article, the synthesis, properties and applications of spin crossover polymer composites, polymers and some related soft materials are reviewed, with a particular attention 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.
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Photo-modulated wide-spectrum chromism in Eu3+ and Eu3+/Tb3+ photochromic coordination polymer gels: application in decoding secret information.

TL;DR: Interestingly, mixed Eu3+/Tb3+ pcCPG exhibited photo-modulated multi-spectrum chromism reversibly where the colour changes from yellow, blue, and red to green and vice versa under suitable light irradiation.
Journal ArticleDOI

A Fluorescence-Detected Coordination-Induced Spin State Switch.

TL;DR: In this paper, the reaction of the spin state to in situ variation of the coordination number (CISSS) is sensitively followed by means of fluorescence detection, and a family of planar nickel(II) complexes with four phenazine-based Schiff base-like ligands were synthesized and characterized through solution-phase spectroscopy (NMR and UV-vis), solidstate structure analysis (single-crystal XRD), and extended theoretical modeling.
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Colossal expansion and fast motion in spin-crossover@polymer actuators.

TL;DR: In this article, a Bilayer Spin Crossover (BSCO) is applied to polymer nanocomposites and the anisotropic shape of the embedded particles as well as the mechanical coupling between the SCO particles and the matrix can substantially intensify the work output of the actuators.
Journal ArticleDOI

The flexibility of long chain substituents influences spin-crossover in isomorphous lipid bilayer crystals.

TL;DR: In this paper, a bent geometry of hexadec-1-ynyl or hexadecyl pyrazole substituents is used to explain the abrupt, stepwise spin-transition on cooling.
References
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Journal ArticleDOI

Synthesis of Spin-Crossover Nano- and Micro-objects in Homogeneous Media

TL;DR: A very promising polymer-free synthetic method is discussed that was based on the preparation of relatively stable Fe(II)-triazole oligomers in CHCl(3) that led to micro-crystals, small nanoparticles, or gels.
Journal ArticleDOI

Size effect in spin-crossover systems investigated by FORC measurements, for surfacted [Fe(NH2-trz)3](Br)2·3H2O nanoparticles: reversible contributions and critical size

TL;DR: In this article, the authors investigated the thermal transition of coated nano-particles of the title compound, on a set of samples of average diameter, with rather broad size distributions, and recorded first-order reversal curves (FORC), the initial parts of which displayed a finite slope, revealing the presence of reversible contributions expected from particles smaller than the critical size associated with the collapse of the hysteresis loop.
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Spin-Crossover Dendrimers: Generation Number-Dependent Cooperativity for Thermal Spin Transition

TL;DR: X-ray diffraction and calorimetric analyses indicated the presence of a discotic columnar core-shell assembly with a crystal lattice best occupied by a C(3)(v)() symmetric array of medium-sized (G1trz)Fe.
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Langmuir-Blodgett Films of Spin Transition Iron(II) Metalloorganic Polymers. 1. Iron(II) Complexes of Octadecyl-1,2,4-triazole

TL;DR: In this paper, a series of iron(II) metalloorganic polymers of 4-octadecyl-1,2,4-triazole has been synthesized.
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Triazole-Based Magnetic Langmuir−Blodgett Films: Paramagnetic to Spin-Crossover Behavior

TL;DR: In this article, the behavior at the air-liquid interface of a series of metal(II) metallo-organic polymers of 4-octadecyl-1,2,4-triazole has been studied.
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Frequently Asked Questions (16)
Q1. What are the contributions mentioned in the paper "Spin crossover polymer composites, polymers and related soft materials" ?

The authors review the synthesis, properties and applications of spin crossover polymer composites, polymers and some related ‘ soft ’ materials. First, the authors 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. 

Dendrimers are globular-shaped, highly branched macromolecules with controlled molecular weight, size and number of functional groups, due to their well-defined synthetic method based on iterative reactions. 

The key interest of this approach is the possibility to create arbitrary planar and threedimensional geometries, which are otherwise not accessible using spin crossover complexes. 

The multiple reactive sites for molecular attachment such as the periphery, core, branching points or cavities in coordination with their micellar properties make dendritic molecules very promising for various applications. 

Mixing polymers with preformed SCO powders (including both micro- and nanocrystals, nanorods, etc.) provides obviously the advantage of better control over particle morphology and SCO properties. 

The SCO nanoparticles were randomly dispersed along the surface of the cellulose fibers - stabilized electrostatically due to the interaction between the hydroxyl groups of the cellulose and the metal cations of the SCO complex. 

The complex [Fe(ODT)3] 2+, with various counter-anions, is probably the most deeply investigated compound capable to form gels in different solvents. 

In this composite, the large strain associated with the spin transition is expected to give rise to an electrical response (voltage or current) due to the piezoelectric properties of the polymer matrix. 

Two parameters were essential to obtain a material with optimal mechanical properties: the nature of the alkoxysilane and the exposure time. 

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. 

They display a change of spin state of iron ions above room temperature, albeit this change is irreversible after the first heating process in all three dendritic Fe(II) complexes, most likely due to the irreversible loss of water molecules ‘bonded’ to the dendritic ligands (through hydrogen bonding etc.). 

It is commonly assumed that these types of compounds are efficient gelators due to lipophilic interactions between the aliphatic part of the SCO complexes and the chosen solvents. 

This effect is more pronounced with the chloride anions due to their inherent small size resulting in a closer chain packing with higher interactions within the bilayers. 

This way they obtained a flexible polymer nanocomposite material with PDMS protection, which provided long-term stability to the material (> 80 days), prevented its decomposition when immersed in hot water and allowed to preserve its SCO properties over >15 thermal cycles. 

The EPR spectra of the PF6 - and Cl- complexes show the presence of three different magnetic iron species (two HS and one LS); while for the ClO4 - only one HS and LS iron center is observed. 

This work is the first example for strain-coupling of SCO to electroactive polymers (EPA) in a composite materials, with interesting perspectives for the development of sensors, actuators and energy harvesting devices.