We studied the effect of light irradiation on the electrical conductance of micro-rods of the spin crossover [Fe(Htrz)2(trz)](BF4) network, organized between interdigitated gold electrodes. By irradiating the sample with different wavelengths (between 295 and 655 nm) either in air or under a nitrogen atmosphere we observed both a reversible and an irreversible change of the current flowing in the device. The reversible process consists of an abrupt decrease of the current intensity (ca. 10-50%) upon light irradiation, while the irreversible process is characterized by a slow, but continuous increase in time of the current, which persists also in the dark. These photo-induced processes were only detected in the high conductance low-spin (LS) state of the complex. On switching the rods to the high spin (HS) state the conductance decreases two orders of magnitude (at the same temperature) and - as a consequence - the photo-effect vanishes.
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http://dx.doi.org/10.1039/c4cp05250a | DOI Listing |
JACS Au
December 2024
Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, IPCM, F-75005 Paris, France.
Metallogels built in a bottom-up approach by metal coordination and supramolecular interactions have important potential for the elaboration of smart materials. In this context, we present here the formation of supramolecular coordination polymers driven by the complexation of cobalt(II) or zinc(II) ions with polyoxometalate-based hybrids displaying two terpyridine ligands in a linear arrangement. Thanks to the electrostatic interactions between the polyoxometalate cores and metal nodes, the polymer chains self-assemble into fibers that physically cross-link to form gels above a critical concentration.
View Article and Find Full Text PDFSmall
December 2024
IMDEA Nanociencia, Ciudad Universitaria de Cantoblanco, C/ Faraday 9, Madrid, 28049, Spain.
Metal-Organic Frameworks (MOFs) attract attention for their intrinsic porosity, large surface area, and functional versatility. To fully utilize their potential in applications requiring precise control at smaller scales, it is essential to overcome challenges associated with their bulk form. This is particularly difficult for 3D MOFs with spin crossover (SCO) behavior, which undergo a reversible transition between high-spin and low-spin states in response to external stimuli.
View Article and Find Full Text PDFJ Phys Condens Matter
December 2024
Department of Physics and Astronomy, University of Nebraska-Lincoln, Jorgenesen Hall, 855 North 16th Street, Lincoln, Nebraska, 68588-0299, UNITED STATES.
Evidence of chirality was observed at the Fe metal center in Fe(III) spin crossover coordination salts [Fe(qsal)Ni(dmit)] and [Fe(qsal)(TCNQ)] from X-ray absorption spectroscopy at the Fe 2pcore threshold. Based on the circularly polarized X-ray absorption data, the X-ray natural circular dichroism seen [Fe(qsal)Ni(dmit)] and [Fe(qsal)(TCNQ)] is far stronger than seen for [Fe(qsal)Cl] suggesting this natural circular dichroism signature is a ligand effect rather than a result of just a loss of octahedral symmetry on the Fe core. The larger the chiral effects in the Fe 2p core to bound X-ray absorption, the greater the perturbation of the Fe 2pto 2pspin-orbit splitting seen in the X-ray absorption spectra.
View Article and Find Full Text PDFChemphyschem
December 2024
Laboratoire de Chimie Quantique, Universit� de Strasbourg, Department of Chemistry, 4 rue Blaise Pascal, 67000, Strasbourg, FRANCE.
Recent, theoretical studies have shown that placing a spin-crossover ion in a field of radical ligands can induce local superpositions of local spin states (see Ref.[1,2]). This phenomenon, termed spinmerism, raises questions about its stability when spin-orbit coupling is included.
View Article and Find Full Text PDFInorg Chem
December 2024
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
Transition metal mechanophores exhibiting force-activated spin-crossover are attractive design targets, yet large-scale discovery of them has not been pursued due in large part to the time-consuming nature of trial-and-error experiments. Instead, we leverage density functional theory (DFT) and external force explicitly included (EFEI) modeling to study a set of 395 feasible Fe and Co mechanophore candidates with tridentate ligands that we curate from the Cambridge Structural Database. Among nitrogen-coordinating low-spin complexes, we observe the prevalence of spin crossover at moderate force, and we identify 155 Fe and Co spin-crossover mechanophores and derive their threshold force for low-spin to high-spin transition ().
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