0000000000270467
AUTHOR
José Alberto Rodríguez-velamazán
Isoreticular two-dimensional magnetic coordination polymers prepared through pre-synthetic ligand functionalization
Chemical functionalization is a powerful approach to tailor the physical and chemical properties of two-dimensional (2D) materials, increase their processability and stability, tune their functionalities and, even, create new 2D materials. This is typically achieved through post-synthetic functionalization by anchoring molecules on the surface of an exfoliated 2D crystal, but it inevitably alters the long-range structural order of the material. Here we present a pre-synthetic approach that allows the isolation of crystalline, robust and magnetic functionalized monolayers of coordination polymers. A series of five isostructural layered magnetic coordination polymers based on Fe(ii) centres a…
Thermal, Pressure and Light Induced Spin Transition in the Two-Dimensional Coordination Polymer [Fe(pmd)2[Cu(CN)2]2]
[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 …
Temperature- and pressure-dependent structural study of {Fe(pmd) 2[Ag(CN)2 ]2}n spin-crossover compound by neutron Laue diffraction
The effect of pressure (up to 0.17GPa) on the spin-crossover compound {Fe(pmd)2[Ag(CN)2]2} n [orthorhombic isomer (II), pmd = pyrimidine] has been investigated by temperature- and pressure-dependent neutron Laue diffraction and magnetometry. The cooperative high-spin ↔ low-spin transition, centred at ca 180K at ambient pressure, is shifted to higher temperatures as pressure is applied, showing a moderate sensitivity of the compound to pressure, since the spin transition is displaced by ca 140KGPa-1. The space-group symmetry (orthorhombic Pccn) remains unchanged over the pressure-temperature (P-T) range studied. The main structural consequence of the high-spin to low-spin transition is the c…
Pulsed-laser switching in the bistability domain of a cooperative spin crossover compound: a critical study through calorimetry
The photoswitching from the low spin (LS) to high spin (HS) state and the reverse process in the bistability domain of spin crossover (SCO) compounds is a promising function to be used in molecular electronic devices, and evidenced mainly through spectroscopy. The phenomenon, and in particular its mechanism, is however still under debate since some controversial experimental results have been reported. Here we present a calorimetric experimental study of the photoswitching of the [Fe(pyrazine)Pt(CN)4] SCO material by a nanosecond-pulsed green laser. Our results confirm that the single laser pulse of varying energies results in significant LS to HS transformations and show that calorimetry p…
Homoleptic iron(II) complexes with the ionogenic ligand 6,6′-Bis(1H-tetrazol-5-yl)-2,2′-bipyridine: spin crossover behavior in a singular 2D spin crossover coordination polymer
Deprotonation of the ionogenic tetradentate ligand 6,6′-bis(1H-tetrazol-5-yl)-2,2′-bipyridine [H2bipy(ttr)2] in the presence of FeII in solution has afforded an anionic mononuclear complex and a neutral two-dimensional coordination polymer formulated as, respectively, NEt3H{Fe[bipy(ttr)2][Hbipy(ttr)2]}·3MeOH (1) and {Fe[bipy(ttr)2]}n (2). The anions [Hbipy(ttr)2]− and [bipy(ttr)2]2– embrace the FeII centers defining discrete molecular units 1 with the FeII ion lying in a distorted bisdisphenoid dodecahedron, a rare example of octacoordination in the coordination environment of this cation. The magnetic behavior of 1 shows that the FeII is high-spin, and its Mössbauer spectrum is characteriz…
Defect-Free Chemical Functionalization of Magnetic Monolayers Based on Coordination Polymers
<p>Chemical functionalization has demonstrated to be a powerful approach to tailor the physical and chemical properties of two-dimensional (2D) materials, to increase their processability and</p> <p>stability, to add new functionalities and, even, to create new 2D materials. However, this post synthetic method – which involves the anchoring of molecules on the surface of an exfoliated 2D crystal – inevitably leads to defective materials, which lack long-range structural order. If defect-free functionalized monolayers are required, a radically new approach needs to be developed. Here we present a pre-synthetic method based on coordination chemistry that affords the isolatio…