Iron(III) Spin Crossover Compounds

Koningsbruggen, Petra J. van; Maeda, Yonezo; Oshio, Hiroki

doi:10.1007/b95409

Cited by 175 publications

(145 citation statements)

References 219 publications

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“…However, our density functional (DFT) calculations of Fe-S vibrations in FeDETEC (not shown) indicate that this absorption band appears to be active in the IR region between 350-240 cm -1 . These calculated results are found to be in excellent agreement with the Fe(III) spin crossover behavior studied by infrared spectroscopy and might be assigned with ν (Fe-S) vibrations 32 .…”

Section: Resultssupporting

confidence: 79%

Nitric oxide release using natural rubber latex as matrix

Herculano

Tzu

Silva³

et al. 2011

Mat. Res.

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Nitric oxide (NO) is a diffusible messenger that has been involved in numerous physiological processes ranging from vasodilatation and antimicrobial properties to wound healing. The beneficial effects can be attributed to the role NO plays in angiogenesis, inflammation and tissue remodeling. In the present work, a polymeric device for the sustained site specific delivery of nitric oxide using a latex rubber matrix from Hevea brasiliensis which encapsulates the spin trap iron(II)-diethyldithiocarbamate complex (FeDETC) was developed. The release profiles of NO from latex rubber matrix were studied and stability studies were carried out. Electron Paramagnetic Resonance (EPR) signal of NO was detected in the membrane exposed to ambient atmosphere at room temperature (25 °C) even after 350 hours. FTIR spectroscopy data indicated that NO-FeDETC retained its structural and spectroscopic properties upon encapsulation in the latex matrix. The NO delivery system developed in this work as a membrane, presented high stability.

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Section: Resultssupporting

confidence: 79%

Nitric oxide release using natural rubber latex as matrix

Herculano

Tzu

Silva³

et al. 2011

Mat. Res.

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“…Most of the published examples focus on iron(II), [4] but iron(III) [5] is also a promising candidate and has the advantage of improved redox stability. [6] tion upon lengthening to C 12 .…”

Section: Introductionmentioning

confidence: 99%

Inducing Spin Crossover in Amphiphilic Iron(III) Complexes

et al. 2010

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“…These structural features are similar to those already reported for different salts and solvates of the same cationic complex. 8 In the LS state the coordination octahedron is much more regular ( The sal 2 -trien ligand wraps the Fe(III) ion in such a way that the two aromatic rings lie approximately in orthogonal planes. Each aromatic ring interacts with an adjacent [Fe(sal 2 -trien)] + cation via p-p stacking defining infinite chains running parallel to the a-axis.…”

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confidence: 99%

[Fe(sal2-trien)][Ni(dmit)2]: towards switchable spin crossover molecular conductors

et al. 2005

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A cooperative spin transition behaviour with a wide hysteresis loop (30 K) around 240 K has been observed, for the first time, in a salt based on the redox active [Ni(dmit) 2 ] 2 , anion and the [Fe(sal 2 -trien)] + spin crossover cation.Supramolecular synthesis of multicomponent materials from spontaneous assembly of molecules into stable and noncovalently joined aggregates is one of the most useful approaches to obtain new functional molecular materials. 1 In this context, spin crossover (SC) building blocks are particularly suitable and represent one of the best examples of molecular bistability. They may be switched between the low-spin (LS) and high-spin (HS) states leading to distinctive changes in magnetism, colour and structure, which may be induced by variation of temperature and/or pressure and by light irradiation. 2 Strong signal generation and hysteresis is observed in some cases when the molecular structural changes associated to SC are cooperatively transmitted in the lattice. 3 Electrical conductivity is a fundamental property of matter currently investigated in the realm of the molecular science. 4 For instance, electronic conduction derived from dithiolene complexbased compounds has received much attention. 5 In particular, compounds of the type (NR 4 ) x [M(dmit) 2 ] (0 , x , 1) with nonintegral oxidation state based on 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit) (NR 4 + 5 tetraalkylammonium cation, M 5 Ni, Pd, Pt) present interesting electric properties. Considering the anionic character of the [Ni(dmit) 2 ] n2 species (Scheme 1, left) and its redox lability as well as the cationic nature and redox stability of most iron(III) SC complexes such as [Fe(sal 2 -trien)] + (Scheme 1, right), 6 we have decided to combine them as building blocks to investigate the possible synergy properties stemming from the coexistence of SC and electronic conduction in the same lattice. 7 As a first step, here we report the synthesis{ and characterisation of the system [Fe(sal 2 -trien)][Ni(dmit) 2 ] (1), which represents the first [Ni(dmit) 2 ] based SC compound.The structure of 1 has been investigated at 295 and 180 K for the HS and LS states, respectively. § Compound 1 is made up of slabs of [Fe(sal 2 -trien)] + cations and layers of [Ni(dmit) 2 ] 2 anions, which alternate along the c-axis and spread out onto the ab plane (Fig. 1). In the HS state, the SC sites are constituted of severely distorted octahedral [FeN 4 O 2 ] centres (Fig. 2, left). The average Fe-N and Fe-O bond distances are 2.155(3) and 1.909(2) s, respectively.The three diagonals of the octahedron, defined by the bonds N(amine)-Fe-O(phenoxo), {N(amine) 5 N2, N3} differ strongly from 180u (155.7(1)-159.0(1)u) while the remaining, defined by N(imine)-Fe-N(imine), is 178.3(1)u {N(imine) 5 N1, N4}. Consequently, the average trigonal distortion W 5 60u 2 H (H is the angle formed by two opposite faces of the octahedron) is 10.9u. These structural features are similar to those already reported for different salts and solvates of the same cationic com...

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Iron(III) Spin Crossover Compounds

Cited by 175 publications

References 219 publications

Nitric oxide release using natural rubber latex as matrix

Nitric oxide release using natural rubber latex as matrix

Inducing Spin Crossover in Amphiphilic Iron(III) Complexes

[Fe(sal2-trien)][Ni(dmit)2]: towards switchable spin crossover molecular conductors

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