Search results for "STATES"
showing 10 items of 1532 documents
Direct monitoring of spin state in dinuclear iron(II) coordination compounds
2001
So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high-spin (HS) and low-spin (LS) species have been deduced from magnetic susceptibility and zero-field Mossbauer spectroscopy data irrespective of whether they belong to LS–LS, LS–HS and HS–HS pairs. However, the distinction of pairs becomes possible if Mossbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.
Thermal, Pressure and Light Induced Spin Transition in the Two-Dimensional Coordination Polymer [Fe(pmd)2[Cu(CN)2]2]
2008
[EN] A complete structural, calorimetric, and magnetic characterisation of the 2D coordination spin crossover polymer {Fe(pmd)(2)[Cu(CN)(2)](2)} is reported. The crystal structure has been investigated below room temperature at 180 K and 90 K, and at 30 K after irradiating the sample at low temperature with green light ( lambda = 532 nm). The volume cell contraction through the thermal spin transition is only 18 angstrom(3) which is lower than the usually observed value of around 25-30 angstrom(3) while the average Fe-N bond distances decrease by the typical value of about 0.19 angstrom. The structural data of the irradiated state indicate that the high spin state is well induced since the …
Pressure-induced cooperative spin transition in ironII 2D coordination polymers: room-temperature visible spectroscopic study.
2011
For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously repo…
Spin-State-Dependent Redox-Catalytic Activity of a Switchable Iron(II) Complex
2017
The spin state of catalytically active 3d metal centers plays a significant role for their activity in enzymatic processes and organometallic catalysis. Here we report on the catalytic activity of a Fe(II) coordination compound that can undergo a cooperative switch between low-spin (LS) and high-spin (HS) states. Catalytic measurements within 291 - 318 K temperature region reveal a drastic drop of the catalytic activity upon conversion of metallic centers from the LS to the HS form. For a thermoswitchable [Fe(NH2trz)3]Br2 complex (Tup = 305 K), an activation energy is found to be considerably lower for the LS state (158 kJ mol-1) comparing to the HS state (305 kJ mol-1). Mossbauer analysis …
Anisotropic Effect after Stretching of the Spin-Crossover Compound [Fe(II)(2,6-bis-(benzimidazol-2′-yl)pyridine)2] (C1O4)2 in Polyvinylalcohol Polyme…
1999
Abstract [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2](C1O4)2 diffused into a poly(vinyl)alcohol polymer matrix, exhibits an thermally induced spin-crossover. After stretching the matrix, the compound orients itself in the matrix. Polarised UV/VIS spectra measured parallel and perpendicular to the stretching direction allowed to calculate the distortion of the molecule in the matrix by means of semi-empirical PPP SCF-CI calculations.
Strong Field Iron(II) Complex Converted by Light into a Long-Lived High-Spin State
2000
Spin Switching with Triazolate-Strapped Ferrous Porphyrins
2019
Fe(III) porphyrins bridged with 1,2,3-triazole ligands were synthesized. Upon deprotonation, the triazolate ion coordinates to the Fe(III) ion, forming an overall neutral high-spin Fe(III) porphyrin in which the triazolate serves both as an axial ligand and as the counterion. The second axial coordination site is activated for coordination and binds p-methoxypyridine, forming a six-coordinate low-spin complex. Upon addition of a phenylazopyridine as a photodissociable ligand, the spin state of the complex can be reversibly switched with ultraviolet and visible light. The system provides the basis for the development of switchable catalase- and peroxidase-type catalysts and molecular spin sw…
Spin-Transition in [Fe(II)(2,6-Bis-(Benzimidazol-2′-yl)pyridine)2] (CIO4)2: Hysteresis Effect Dependent on the Matrix
1999
Abstract Far-Infrared spectroscopical investigation of the spin-crossover in [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2] (CIO4)2 exhibits a hysteresis in both CsI and polyethylene matrices within temperature cycles between 100K and 520K. The hysteresis broadening is dependent on the matrix and bigger in CsI. This can be explained due to polarity and hydrogen bonding. Two low spin vibrations, LS1 at 437 cm−1 and LS2 at 424cm−1, are observed. On heating from 100K to 520K: during LS1 decreases, the LS2 raises temporarily, until both LS1 and LS2 disappear; for the HS only one raising species was observed. This gives raise to assume two different sub-lattices.
Bidirectional Chemo-Switching of Spin State in a Microporous Framework
2009
The ins and outs of spin: Using the microporous coordination polymer {Fe(pz)[Pt(CN)(4)]} (1, pz=pyrazine), incorporating spin-crossover subunits, two-directional magnetic chemo-switching is achieved at room temperature. In situ magnetic measurements following guest vapor injection show that most guest molecules transform 1 from the low-spin (LS) state to the high-spin (HS) state, whereas CS(2) uniquely causes the reverse HS-to-LS transition.