Search results for "CROSSOVER"
showing 10 items of 658 documents
Selective Photoswitching of the Binuclear Spin Crossover Compound{[Fe(bt)(NCS)2]2(bpm)}into Two Distinct Macroscopic Phases
2005
The low-spin (LS-LS, $S=0$) diamagnetic form of the binuclear spin crossover complex ${[\mathrm{Fe}(\mathrm{bt})(\mathrm{NCS}{)}_{2}{]}_{2}(\mathrm{bpm})}$ was selectively photoconverted into two distinct macroscopic phases at different excitation wavelengths (1342 or 647.1 nm). These long-lived metastable phases have been identified, respectively, as the symmetry-broken paramagnetic form (HS-LS, $\mathrm{S}=2$) and the antiferromagnetically coupled (HS-HS, $S=0$) high-spin form of the compound. The selectivity may be explained by the strong coupling of the primary excited states to the paramagnetic state.
Structural phase transition to disorder low-temperature phase in [Fe(ptz)6](BF4)2 spin-crossover compounds.
2012
In the spin-crossover compound [Fe(ptz)6](BF4)2 (where ptz=1-n-propyltetrazole) six different phases are observed. When a single crystal is slowly cooled from high temperatures to those below 125 K, the reflections broaden into diffuse maxima and split into two maxima along the c* direction [Kusz, Gütlich & Spiering (2004). Top. Curr. Chem. 234, 129–153]. As both maxima are broad along the c* direction, the short-range order exists only along the c direction and in the ab plane the structure remains long-range ordered. In this disordered phase additional satellite reflections appear. Upon heating above 135 K, the diffuse maxima return to their previous shape and this process is complete…
Polymorphism and “reverse” spin transition in the spin crossover system [Co(4-terpyridone)2](CF3SO3)2·1H2O
2009
[EN] Compound [Co(4-terpyridone)(2)](CF3SO3)(2)center dot 1H(2)O, where 4-terpyridone is 2,6-bis(2-pyridyl)-4(1H)-pyridone, forms two polymorphs. Polymorph 1 displays a continuous spin conversion in the temperature region 300-120 K while polymorph 2 shows, on cooling, the onset of a continuous high-spin (HS) to low-spin (LS) conversion interrupted by an abrupt "reverse'' spin transition in the temperature region 217-203 K. The formed unstable HS intermediate phase (IP) undergoes a strong cooperative "normal'' spin transition characterised by a hysteresis loop 33 K wide. The structural data give support for a crystallographic phase transition, which takes place concomitantly with the "revers…
Contribution of X-Ray diffraction to the study of spin transitions in some iron (II) complexes
1991
Abstract A review of recent single crystal investigations under constraint of iron (II) spin crossover complexes is given. The systems covered are Fe L2 (NCS)2 complexes (L = Phen, Btz) and some analogous derivatives. Emphasis is laid on the correlations between structural changes associated with spin transitions and the experimentally determined characteristics of these transitions.
Interplay of Antiferromagnetic Coupling and Spin Crossover in Dinuclear Iron(II) Complexes
2003
This article reports on the study of the interplay between magnetic coupling and spin transition in 2,2′-bipyrimidine (bpym)-bridged iron(II) dinuclear compounds. Coexistence of both phenomena has been observed in [Fe(bpym)(NCS)2]2bpym, [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym (bpym = 2,2′-bipyrimidine, bt = 2,2′-bithiazoline) by the action of external physical factors namely pressure or electromagnetic radiation. Competition between magnetic exchange and spin crossover has been studied in [Fe(bpym)(NCS)2]2bpym at 6.3 kbar. LIESST experiments carried out in [Fe(bpym)(NCSe)2]2bpym and [Fe(bt)(NCS)2]2bpym at 4.2 K have shown that is possible to achieve dinuclear molecules with different…
Mixed spin-state [HS-LS] pairs in a dinuclear spin-transition complex: confirmation by variable-temperature 57Fe Mössbauer spectroscopy.
2008
Exquisite sensitivity of Mossbauer spectroscopy for tiny local molecular distortion is demonstrated in [FeII2(pmat)2](BF4)4?DMF: high-spin (HS) iron(II) in [HS-HS] and in [LS-HS] (low-spin–high-spin) pairs is clearly distinguished (see picture) for the first time without the need to apply a magnetic field. This dinuclear complex clearly shows that spin crossover via a [LS-HS] species is promoted by the use of a highly constrained bridging ligand (the bis-terdentate pmat).
X-ray structure study of the light-induced metastable states of the spin-crossover compound [Fe(mtz)6](BF4)2
2001
Iron(II) complexes exhibiting thermal spin-crossover may be converted from the1A1low-spin (LS) state to the5T2high-spin (HS) state by irradiation with green light (light-induced excited spin-state trapping, LIESST) and from the LS to the HS state by irradiation with red light (reverse LIESST). The lifetime of the metastable LIESST states may be sufficiently long to enable an X-ray diffraction study. The lattice parameters of a single crystal of [Fe(mtz)6](BF4)2(mtz = methyltetrazole) (space groupP21/n) were measured between 300 and 10 K. While one Fe lattice site (A) of the crystal changes from the HS to the LS state near 78 K, the other site (B) remains in the LS state. Using the green lig…
Spin Transitions in Iron(II) Complexes
1996
Iron(II) has the 3d6 outer electronic configuration and hence its octahedral complexes may be either high-spin or low-spin. The high-spin configuration, t 2g 4 e g 2 , is adopted when relatively weak-field ligands are coordinated while the low-spin, t 2g 6 e g 0 , is obtained when strong-field ligands are involved. In Oh symmetry the ground states are 5T2g and lA1g, for the high-spin and low-spin configurations, respectively. While in most iron(II) six-coordinate complexes the symmetry is lower than Oh, these designations are generally adopted in the following sections for convenience. [Fe(H2O)6]2+ and [Fe(en)3]2+ (en = ethylenediamine) are typical examples of high-spin complexes, while [Fe…
Mixed-Valence, Mixed-Spin-State, and Heterometallic [2×2] Grid-type Arrays Based on Heteroditopic Hydrazone Ligands: Synthesis and Electrochemical Fe…
2005
Une famille de complexes heterometalliques [M 1 2 M 2 2 (L - ) 4 ] n + du type grille [2×2] 1-9 a ete preparee. Les trois approches synthetiques multietapes des ligands hydrazone heteroditopiques A-C possedent chacune des caracteristiques regio-, redox-, enantio-selectives. Ces ligands possedent un groupement NH ionisable et un groupement hydrazone non-ionisable NMe, qui permettent un controle des proprietes redox du metal complexe en fonction de la charge de la cavite coordinante. Les substituants 2-pyrimidine (R) et 6-pyridine (R') influencent de maniere significative la geometrie des complexes formes ainsi que leurs proprietes electrochimiques et magnetiques. Les etudes par spectroscopie…
New polynuclear 4,4ˈ-bis-1,2,4-triazole Fe(II) spin crossover compounds
2001
L'interet porte aux materiaux moleculaires du Fe(II) presentant une transition entre un etat haut-spin (HS, S = 2) et un etat bas-spin (LS, S = 0), sous l'effet d'une variation de temperature, de pression ou d'une irradiation lumineuse, n'a cesse de croitre au cours de ces dix dernieres annees [1-4]. La famille des composes du Fe(II) a base de derives du 1,2,4-triazole substitues par un groupe R sur l'azote 4 a ete tres etudiee pour ses proprietes de transition de spin (TS), qui pourraient permettre des applications en electronique moleculaire [5-15, 29, 32, 36, 37]. Nous avons recemment presente le premier compose a TS possedant une structure tridimensionnelle (figure 2). Ce compose de for…