The Fe(II) spin crossover complex [Fe{H B(pz) } (bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine) can be locked in a largely low-spin-state configuration over a temperature range that includes temperatures well above the thermal spin crossover temperature of 160 K. This locking of the spin state is achieved for nanometer thin films of this complex in two distinct ways: through substrate interactions with dielectric substrates such as SiO and Al O , or in powder samples by mixing with the strongly dipolar zwitterionic p-benzoquinonemonoimine C H (-⋯ NH ) (-⋯ O) . Remarkably, it is found in both cases that incident X-ray fluences then restore the [Fe{H B(pz) } (bipy)] moiety to an electronic state characteristic of the high spin state at temperatures of 200 K to above room temperature; that is, well above the spin crossover transition temperature for the pristine powder, and well above the temperatures characteristic of light- or X-ray-induced excited-spin-state trapping. Heating slightly above room temperature allows the initial locked state to be restored. These findings, supported by theory, show how the spin crossover transition can be manipulated reversibly around room temperature by appropriate design of the electrostatic and chemical environment.
Voltage-controlled room temperature isothermal reversible spin crossover switching of [Fe{H 2 B(pz) 2 } 2 (bipy)] thin films is demonstrated. This isothermal switching is evident in thin film bilayer structures where the molecular spin crossover film is adjacent to a molecular ferroelectric. The adjacent molecular ferroelectric, either polyvinylidene fluoride hexafluoropropylene or croconic acid (C 5 H 2 O 5), appears to lock the spin crossover [Fe{H 2 B(pz) 2 } 2 (bipy)] molecular complex largely in the low or high spin state depending on the direction of ferroelectric polarization. In both a planar two terminal diode structure and a transistor structure, the voltage controlled isothermal reversible spin crossover switching of [Fe{H 2 B(pz) 2 } 2 (bipy)] is accompanied by a resistance change and is seen to be nonvolatile, i.e., retained in the absence of an applied electric field. The result appears general, as the voltage controlled nonvolatile switching can be made to work with two different molecular ferroelectrics: croconic acid and polyvinylidene fluoride hexafluoropropylene.
The spin crossover (SCO) transitions at both the surface and over the entire volume of the [Fe{H2B(pz)2}2(bipy)] polycrystalline films on Al2O3 substrates have been studied, where pz = pyrazol-1-yl and bipy = 2,2′-bipyridine. For [Fe{H2B(pz)2}2(bipy)] films of hundreds of nm thick, magnetometry and x-ray absorption spectroscopy measurements show thermal hysteresis in the SCO transition with temperature, although the transition in bulk [Fe{H2B(pz)2}2(bipy)] occurs in a non-hysteretic fashion at 157 K. While the size of the crystallites in those films are similar, the hysteresis becomes more prominent in thinner films, indicating a significant effect of the [Fe{H2B(pz)2}2(bipy)]/Al2O3 interface. Bistability of spin states, which can be inferred from the thermal hysteresis, was directly observed using temperaturedependent x-ray diffraction; the crystallites behave as spin-state domains that coexist during the transition. The difference between the spin state of molecules at the surface of the [Fe{H2B(pz)2}2(bipy)] films and that of the molecules within the films, during the thermal cycle, indicates that both cooperative (intermolecular) effects and coordination are implicated in perturbations to the SCO transition.
Room temperature isothermal reversible spin crossover switching of [Fe(HB(pz))(bipy)] thin films is demonstrated. The magnetic oxide substrate locks the [Fe{HB(pz)}(bipy)] largely in a low spin state. With an X-ray fluence, excitation to a high spin state occurs, while relaxation back to low spin state is aided by alternating the substrate magnetization.
Nonvolatile, molecular multiferroic devices have now been demonstrated, but it is worth giving some consideration to the issue of whether such devices could be a competitive alternative for solid-state nonvolatile memory. For the Fe (II) spin crossover complex [Fe{H2B(pz)2}2(bipy)], where pz = tris(pyrazol-1-yl)-borohydride and bipy = 2,2′-bipyridine, voltage-controlled isothermal changes in the electronic structure and spin state have been demonstrated and are accompanied by changes in conductance. Higher conductance is seen with [Fe{H2B(pz)2}2(bipy)] in the high spin state, while lower conductance occurs for the low spin state. Plausibly, there is the potential here for low-cost molecular solid-state memory because the essential molecular thin films are easily fabricated. However, successful device fabrication does not mean a device that has a practical value. Here, we discuss the progress and challenges yet facing the fabrication of molecular multiferroic devices, which could be considered competitive to silicon.
Ferroelectricity at room temperature has been demonstrated in nanometer-thin quasi 2D croconic acid thin films, by the polarization hysteresis loop measurements in macroscopic capacitor geometry, along with observation and manipulation of the nanoscale domain structure by piezoresponse force microscopy. The fabrication of continuous thin films of the hydrogen-bonded croconic acid was achieved by the suppression of the thermal decomposition using low evaporation temperatures in high vacuum, combined with growth conditions far from thermal equilibrium. For nominal coverages ≥20 nm, quasi 2D and polycrystalline films, with an average grain size of 50-100 nm and 3.5 nm roughness, can be obtained. Spontaneous ferroelectric domain structures of the thin films have been observed and appear to correlate with the grain patterns. The application of this solvent-free growth protocol may be a key to the development of flexible organic ferroelectric thin films for electronic applications.Recent reports of room temperature ferroelectricity in croconic acid, 1 related oxocarbons, 2 benzimidazoles 3 , and related hydrogen-bonded proton transfer systems 2 are currently accelerating the emergence of molecular ferroelectrics (MFE) as viable materials alternatives to inorganic ferroelectrics, such as the prototypical barium titanate, BaTiO3. Importantly, croconic acid (CA), C5O5H2, exhibits room temperature polarization of the order of 10 -20 C/cm 2 in bulk crystals, which is comparable to that of BaTiO3, while at the same time the polarization switching fields are of practical order of magnitude. 3 The ferroelectric behavior of proton transfer organics like CA emerges from the resonance-assisted hydrogen bonding, specifically from the strong coupling between the protons in the hydrogen bonds and the π-electron system of the molecules that give them their dipole moments. 4MFEs have distinctive advantages over complex oxides and may replace oxides in some applications, with benefits in terms of flexibility, scalability, and sustainability. [5][6][7] The potential of MFEs to become viable material alternatives to inorganic ferroelectrics hinges on the availability of strategies to fabricate thin films with defined structure and morphology on a large scale, which at the same time preserve their ferroelectric properties. Vapor deposition, especially chemical vapor deposition polymerization, has been a method of choice for the fabrication of thin films of numerous organic polymers, including the popular ferroelectric polyvinylidene fluoride, PVDF. 8,9 However, previous work has ruled out, the possibility to utilize thermal evaporation growth techniques for CA because the decomposition temperature is lower than the melting point (177 °C). Another challenge is that the film growth tends to be three-dimensional, due to the weak interaction between the MFEs and most non-reactive inorganic substrates. Matrix-assisted pulsed laser deposition was performed as an alternative strategy for croconic acid thin films (100-200 nm thick), but without...
A mononuclear complex [Fe(tBu 2 qsal) 2 ] has been obtained by a reaction between an Fe(II) precursor salt and a tridentate ligand 2,4-di(tert-butyl)-6-((quinoline-8-ylimino)methyl)phenol (tBu 2 qsalH) in the presence of triethylamine. The complex exhibits a hysteretic spin transition at 117 K upon cooling and 129 K upon warming, as well as light-induced excited spinstate trapping at lower temperatures. Although the strongly cooperative spin transition suggests substantial intermolecular interactions, the complex is readily sublimable, as evidenced by the growth of its single crystals by sublimation at 573 → 373 K and ∼10 −3 mbar. This seemingly antagonistic behavior is explained by the asymmetric coordination environment, in which the tBu substituents and quinoline moieties appear on opposite sides of the complex. As a result, the structure is partitioned in well-defined layers separated by van der Waals interactions between the tBu groups, while the efficient cooperative interactions within the layer are provided by the quinoline-based moieties. The abrupt spin transition is preserved in a 20 nm thin film prepared by sublimation, as evidenced by abrupt and hysteretic changes in the dielectric properties in the temperature range comparable to the one around which the spin transition is observed for the bulk material. The changes in the dielectric response are in excellent agreement with differences in the dielectric tensor of the low-spin and high-spin crystal structures evaluated by density functional theory calculations. The substantially higher volatility of [Fe(tBu 2 qsal) 2 ], as compared to a similar complex without tBu substituents, suggests that asymmetric molecular shapes offer an efficient design strategy to achieve sublimable complexes with strongly cooperative spin transitions.
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