The bistability of spin-crossover complexes on surfaces is of great interest for potential applications. Using x-ray absorption spectroscopy, we investigated the properties of [Fe(pypyr(CF 3) 2) 2 (phen)] (pypyr = 2-(2'-pyridyl)pyrrolide, phen = 1,10-phenanthroline), a vacuum-evaporable Fe(II) complex, in direct contact to a set of substrates. The electronic properties of these substrates range from metallic to semiconducting. While dissociation is observed on metal surfaces, efficient light-induced switching is realized on semimetallic and semiconducting surfaces. This indicates that the density of states of the substrate at the Fermi level plays a role for the integrity and functionality of the adsorbed compound. In an intermediate case, namely [Fe(pypyr(CF 3) 2) 2 (phen)] on graphene/Ni(111), functional and dissociated species are found to coexist. This result indicates that some previous studies may deserve to be reconsidered because the possibility of coexisting intact and fragmented spin-crossover complexes was neglected.
Understanding and controlling the spin-crossover properties of molecular complexes can be of particular interest for potential applications in molecular spintronics. Using near-edge X-ray absorption fine structure spectroscopy, we investigated these properties for a new vacuum-evaporable Fe(II) complex, namely [Fe(pypyr(CF))(phen)] (pypyr = 2-(2'-pyridyl)pyrrolide, phen = 1,10-phenanthroline). We find that the spin-transition temperature, well above room temperature for the bulk compound, is drastically lowered for molecules arranged in thin films. Furthermore, while within the experimentally accessible temperature range (2 K < T < 410 K) the bulk material shows indication of neither light-induced excited spin-state trapping nor soft X-ray-induced excited spin-state trapping, these effects are observed for molecules within thin films up to temperatures around 100 K. Thus, by arranging the molecules into thin films, a nominal low-spin complex is effectively transformed into a spin-crossover complex.
Echolocating bats can identify three-dimensional objects exclusively through the analysis of acoustic echoes of their ultrasonic emissions. However, objects of the same structure can differ in size, and the auditory system must achieve a size-invariant, normalized object representation for reliable object recognition. This study describes both the behavioral classification and the cortical neural representation of echoes of complex virtual objects that vary in object size. In a phantom-target playback experiment, it is shown that the bat Phyllostomus discolor spontaneously classifies most scaled versions of objects according to trained standards. This psychophysical performance is reflected in the electrophysiological responses of a population of cortical units that showed an object-size invariant response (14/109 units, 13%). These units respond preferentially to echoes from objects in which echo duration (encoding object depth) and echo amplitude (encoding object surface area) co-varies in a meaningful manner. These results indicate that at the level of the bat's auditory cortex, an object-oriented rather than a stimulus-parameter–oriented representation of echoes is achieved.
The (pypz)) 2 ] (py = pyridine, pz = pyrazole) deposited on Ag(111) was investigated with scanning tunneling microscopy at � 5 K. Due to a bis(tridentate) coordination sphere the molecules aggregate mainly into tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors. Two molecules exhibit this bistability while the other two molecules are stable. The transition rates vary linearly with the tunneling current and exhibit an intriguing dependence on the bias voltage and its polarity. We interpret the states as being due to S = 1 / 2 and 3 / 2 spin states of the Co 2 + complex. The image contrast and the orders-of-magnitude variations of the switching yields can be tentatively understood from the calculated orbital structures of the two spin states, thus providing first insights into the mechanism of electron-induced excited spinstate trapping (ELIESST).
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