A magnetic iron(iii) switch with controlled and adjustable thermal response for solution processing

Gandolfi, Claudio; Morgan, Grace G.; Albrecht, Martin

doi:10.1039/c2dt12037b

Cited by 40 publications

(35 citation statements)

References 50 publications

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“…An analogous effect should also apply for the record player design. This is why we set out to synthesize record player #2 with electron withdrawing pentafluorophenyl substituents (2) in the three available meso positions. The syntheses and a rough characterisation were presented previously.…”

Section: Computational Modelingmentioning

confidence: 99%

Rational design of a room temperature molecular spin switch. The light-driven coordination induced spin state switch (LD-CISSS) approach

et al. 2014

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Extensive use of quantum chemical calculations has been made to rationally design a molecule whose spin state can be switched reversibly using light of two different wavelengths at room temperature in solution. Spin change is induced by changing the coordination number of a nickel complex. The coordination number in turn is switched using a photochromic ligand that binds in one configuration and dissociates in the other. We demonstrate that successful design relies on a precise geometry fit and delicate electronic tuning. Our designer complex exhibits an extremely high long-term switching stability (more than 20 000 cycles) and a high switching efficiency. The high-spin state is extraordinarily stable with a half-life of 400 days at room temperature. Switching between the dia-and paramagnetic state is achieved with visible light (500 and 430 nm). The compound can also be used as a molecular logic gate with light and pH as input and the magnetic state as non-destructive read-out.

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Section: Computational Modelingmentioning

confidence: 99%

Rational design of a room temperature molecular spin switch. The light-driven coordination induced spin state switch (LD-CISSS) approach

et al. 2014

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“…This could result in liquid crystalline behaviour of the material, where synergetic effects between phase transition and spin transition (ST) are possible 6–12. Another interesting aspect is the self‐assembly of such complexes in solution that might lead to the formation of micelles or inverse micelles and can influence the ST properties in solution 13. 14 Further the self‐assembly of amphiphilic complexes on frontiers can be used for the formation of Langmuir–Blodgett (LB) films 15.…”

Section: Introductionmentioning

confidence: 99%

Influence of the Alkyl Chain Length on the Self‐Assembly of Amphiphilic Iron Complexes: An Analysis of X‐ray Structures

Schlamp

Thoma

Weber

2014

Chemistry A European J

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Several new amphiphilic iron complexes were synthesised and characterised by single crystal X-ray structure analysis. The Schiff-base-like equatorial ligands contain long alkyl chains in their outer periphery with chain lengths of 8, 12, 16 and 22 carbon atoms. As axial ligands methanol, pyridine, 4-aminopyridine, 4-(dimethylamino)pyridine and 1,2-bis(4-pyridyl)ethane were used. X-ray structure analysis of the products reveals different coordination numbers, depending on the combination of equatorial and axial ligand. The driving force for this is the self-assembly to lipid-layer-like arrangements. This can be controlled through the chain lengths and the dimension of the axial ligands in a crystal-engineering-like approach. For this an empirical rule is introduced concerning the crystallisation behaviour of the complexes. The efficacy of this rule is confirmed with the crystallisation of an octahedral complex with two docosyl (C22) chains in the outer periphery. The rule is also applied to other ligand systems.

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“…In solution, the distribution of spin states is assigned using a Boltzmann distribution, and a spin equilibrium is expected at different temperatures. However, depending on the nature of the ligand used, interactions between molecules may occur and SCO systems with different degrees of communication between metal centers have sometimes been reported [50][51][52][53][54][55]. The molecules deposited on supports have been subjected to electric fields to produce systems that change their spin state by an application of a more suitable stimulus towards application into spintronics [47][48][49][56][57][58][59][60].…”

mentioning

confidence: 99%

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

2020

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The capability of a given substance to change its spin state by the action of a stimulus, such as a change in temperature, is by itself a very challenging property. Its interest is increased by the potential applications and the need to find sustainable functional materials. 3D transition metal complexes, mainly with octahedral geometry, display this property when coordinated to particular sets of ligands. The prediction of this behavior has been attempted by many authors. It is, however, made very difficult because spin crossover (SCO), as it is called, occurs most often in the solid state, where besides complexes, counter ions, and solvents are also present in many cases. Intermolecular interactions definitely play a major role in SCO. In this review, we decided to analyze SCO in mono- and binuclear transition metal complexes containing halogens as ligands or as substituents of the ligands. The aim was to try and find trends in the properties which might be correlated to halogen substitution patterns. Besides a revision of the properties, we analyzed structures and other information. We also tried to build a simple model to run Density Functional Theory (DFT) calculations and calculate several parameters hoping to find correlations between calculated indices and SCO data. Although there are many experimental studies and single-crystal X-ray diffraction structures, there are only few examples with the F, Cl, Br and series. When their intermolecular interactions were not very different, T1/2 (temperature with 50% high spin and 50% low spin states) usually increased with the calculated ligand field parameter (Δoct) within a given family. A way to predict SCO remains elusive.

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A magnetic iron(iii) switch with controlled and adjustable thermal response for solution processing

Cited by 40 publications

References 50 publications

Rational design of a room temperature molecular spin switch. The light-driven coordination induced spin state switch (LD-CISSS) approach

Rational design of a room temperature molecular spin switch. The light-driven coordination induced spin state switch (LD-CISSS) approach

Influence of the Alkyl Chain Length on the Self‐Assembly of Amphiphilic Iron Complexes: An Analysis of X‐ray Structures

Spin Crossover in 3D Metal Centers Binding Halide-Containing Ligands: Magnetism, Structure and Computational Studies

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