Different kinds of stimuli to induce spin crossover in iron compounds are covered, focusing on electromagnetic irradiation-induced spin state switching phenomena in mono- as well as multinuclear coordination compounds.

Improving the graphitic structure in carbon nanofibers (CNFs) is important for exploiting their potential in mechanical, electrical and electrochemical applications. Typically, the synthesis of carbon fibers with a highly graphitized structure demands a high temperature of almost 2500 °C. Furthermore, to achieve an improved graphitic structure, the stabilization of a precursor fiber has to be assisted by the presence of tension in order to enhance the molecular orientation. Keeping this in view, herein we report on the fabrication of graphene nanoplatelets (GNPs) doped carbon nanofibers using electrospinning followed by oxidative stabilization and carbonization. The effect of doping GNPs on the graphitic structure was investigated by carbonizing them at various temperatures (1000 °C, 1200 °C, 1500 °C and 1700 °C). Additionally, a stabilization was achieved with and without constant creep stress (only shrinkage stress) for both pristine and doped precursor nanofibers, which were eventually carbonized at 1700 °C. Our findings reveal that the GNPs doping results in improving the graphitic structure of polyacrylonitrile (PAN). Further, in addition to the templating effect during the nucleation and growth of graphitic crystals, the GNPs encapsulated in the PAN nanofiber matrix act in-situ as micro clamp units performing the anchoring function by preventing the loss of molecular orientation during the stabilization stage, when no external tension is applied to nanofiber mats. The templating effect of the entire graphitization process is reflected by an increased electrical conductivity along the fibers. Simultaneously, the electrical anisotropy is reduced, i.e., the GNPs provide effective pathways with improved conductivity acting like bridges between the nanofibers resulting in an improved conductivity across the fiber direction compared to the pristine PAN system.

We synthesized iron(II)-triazole spin crossover compounds of the type [Fe(atrz)₃]X₂ and incorporated and deposited them on electrospun polymer nanofibers. For this, we used two separate electrospinning methods with the goal of obtaining polymer complex composites with intact switching properties. In view of possible applications, we chose iron(II)-triazole-complexes that are known to exhibit spin crossover close to ambient temperature. Therefore, we used the complexes [Fe(atrz)₃]Cl₂ and [Fe(atrz)₃](2ns)₂ (2ns = 2-Naphthalenesulfonate) and deposited those on fibers of polymethylmethacrylate (PMMA) and incorporated them into core–shell-like PMMA fiber structures. These core–shell structures showed to be inert to outer environmental influences, such as droplets of water, which we purposely cast on the fiber structure, and it did not rinse away the used complex. We analyzed both the complexes and the composites with IR-, UV/Vis, Mössbauer spectroscopy, SQUID magnetometry, as well as SEM and EDX imaging. The analysis via UV/Vis spectroscopy, Mössbauer spectroscopy, and temperature-dependent magnetic measurements with the SQUID magnetometer showed that the spin crossover properties were maintained and were not changed after the electrospinning processes.

In addition to the chemical and physical properties of nanostructures their successful utilization for applications is strongly triggered by economic aspects. Electrospinning of nanowires from solution followed by subsequent annealing steps is a comparably cheap technique to fabricate conductive carbon nanofibers (CNF) made from polyacrylonitrile (PAN) molecules in large quantities. In this work, we investigated the microscopic properties of the CNFs with diameters of 100–300 nm by means of Raman and x-ray photoelectron spectroscopy and correlated these results with transport measurements done with a 4-tip STM. In particular, we investigated the effect of fiber alignment and knot densities, which can be controlled by applying constant creep due to stress during the stabilization process. The comparison of the conductivity obtained from single CNFs revealed further that the fiber crossings within the ensemble structure act as scattering centers and proofs that the transport is along the surfaces of the CNFs.