0000000000073841
AUTHOR
Christophe Faulmann
Towards Molecular Conductors with a Spin‐Crossover Phenomenon:Crystal Structures, Magnetic Properties and Mössbauer Spectra of[Fe(salten)Mepepy][M(dmit) 2 ] Complexes
Three new iron(III) compounds of formula [Fe(salten)Mepepy][M(dmit)2]·CH3CN (M = Ni, Pd, Pt; H2salten = 4-azaheptamethylene-1,7-bis(salicylideneiminate); Mepepy = 1-(pyridin-4-yl)-2-(N-methylpyrrol-2-yl) ethane; dmit2– = 1,3-dithiole-2-thione-4,5-dithiolato) have been synthesised and the crystal structure of each compound has been solved at different temperatures. The structures consist of alternating layers of [M(dmit)2]– units and [Fe(salten)Mepepy] cations. In the Ni compound photo-isomerisation of the Mepepy ligand can be observed in dichloromethane solution. The temperature dependence of the magnetic susceptibility of the compounds reveals a gradual S = 5/2 blabla S = 1/2 spin crossove…
Ferromagnetism in [Mn(Cp*) 2 ] + ‐Derived Complexes: the “Miraculous” Stacking in [Mn(Cp*) 2 ][Ni(dmit) 2 ]
The synthesis and characterisation (X-ray structure and magnetism) of metal complexes (Ni, Au) with the [Mn(Cp*)2]+ cation and the dmit2− and dmid2− ligands are reported. [Mn(Cp*)2][Ni(dmit)2] (1) and [Mn(Cp*)2][Au(dmit)2] (2) exhibit the same structural arrangement, built on stacks of [Ni(dmit)2]− pairs separated by two [Mn(Cp*)2]+ cations, showing a ···D+D+A−A−D+D+A−A−··· motif. On the contrary, the dmid2− derivative [Mn(Cp*)2][Ni(dmid)2]·CH3CN (3) exhibits a totally different structure, built on mixed layers composed of one [Ni(dmid)2]− unit separated by two [Mn(Cp*)2]+ cations, showing a ···D+D+A−D+D+A−···motif. The layers are separated from each other by perpendicular [Ni(dmid)2]− unit…
Synthesis, crystal structures and magnetic properties of mononuclear tris(croconate)ferrate(III) complexes
Abstract A straightforward synthetic method to prepare mononuclear croconato-containing iron (III) complexes, (A)3[Fe(C5O5)3] [A = tetrabutylammonium = n-Bu4N+ (1) and tetraphenylphosphonium = PPh 4 + ( 2 ) ; C 5 O 5 2 - = croconate = dianion of 4 , 5 - dihydroxycyclopent - 4 - ene - 1 , 2 , 3 - trione ] along with their crystal structures and magnetic properties, are reported. The Fe(III) atom adopts a pseudo-octahedral geometry while magnetic susceptibility measurements, in the 2–300 K temperature range, show the occurrence of a high spin state (S = 5/2) in both complexes.
New BEDT-TTF/[Fe(C5O5)3]3- Hybrid System: Synthesis, Crystal Structure, and Physical Properties of a Chirality-Induced α Phase and a Novel Magnetic Molecular Metal
The paramagnetic and chiral anion [Fe(C5O5)3]3- (C5O52-=croconate) has been combined with the organic donor BEDT-TTF (=ET=bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced alpha phase, alpha-(BEDT-TTF)5[Fe(C5O5)3].5H2O (1), and one of the few known paramagnetic molecular metals, beta-(BEDT-TTF)5[Fe(C5O5)3].C6H5CN (2). Both compounds present layers of BEDT-TTF molecules, with the alpha or beta packing modes, alternating with layers containing the high-spin S=5/2 Fe(III) anions and solvent molecules. In the alpha phase, the alternation of the chiral [Fe(C5O5)3]3- anions along the direction perpendicular to the BEDT-TTF cha…
A chirality-induced alpha phase and a novel molecular magnetic metal in the BEDT-TTF/tris(croconate)ferrate(iii) hybrid molecular system
The novel paramagnetic and chiral anion [Fe(C5O5)3]32 has been combined with the organic donor BEDT-TTF (= ET = bis(ethylenedithio)tetrathiafulvalene) to yield the first chirality- induced α phase and a paramagnetic metal. Gomez Garcia, Carlos, Carlos.Gomez@uv.es ; Coronado Miralles, Eugenio, Eugenio.Coronado@uv.es ; Gimenez Saiz, Carlos, Carlos.Gimenez@uv.es
Temperature and pressure effects on the spin state of ferric ions in the [Fe(sal2-trien)][Ni(dmit)2] spin crossover complex
Abstract Thermal and pressure effects have been investigated on the [Fe(sal 2 -trien)][Ni(dmit) 2 ] spin crossover complex by means of Mossbauer spectroscopic, calorimetric, X-ray diffraction and magnetic susceptibility measurements. The complex displays a complete thermal spin transition between the S = 5 2 and S = 1 2 spin states of Fe III near 245 K with a hysteresis loop of ca. 30 K. This transition is characterised by a change of the enthalpy, Δ H HL =7 kJ/mol, entropy, Δ S HL =29 J/Kmol, and the unit cell volume, Δ V HL =15.4 A 3 . Under hydrostatic pressures up to 5.7 kbar the thermal transition shifts to higher temperatures by ca. 16 K/kbar. Interestingly, at a low applied pressure …
Crystal structure, magnetic properties and Mössbauer studies of [Fe(qsal)2][Ni(dmit)2]
Abstract A new compound of formula [Fe(qsal)2][Ni(dmit)2] (1) has been synthesised, structurally and magnetically characterised (qsalH = N-(8-quinolyl)salicylaldimine, dmit2− = 1,3-dithiol-2-thione-4,5-dithiolato). Its structural features and its magnetic behaviour were compared with those of [Fe(qsal)2]-based complexes, and more particularly [Fe(qsal)2][Ni(dmit)2] · 2CH3CN.
[Fe(sal2-trien)][Ni(dmit)2]: towards switchable spin crossover molecular conductors
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]¯, anion and the [Fe(sal2-trien)]+ spin crossover cation. Real Cabezos, Jose Antonio, Jose.A.Real@uv.es