| People | Locations | Statistics |
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| Naji, M. |
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| Motta, Antonella |
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| Aletan, Dirar |
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| Mohamed, Tarek |
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| Ertürk, Emre |
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| Taccardi, Nicola |
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| Kononenko, Denys |
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| Petrov, R. H. | Madrid |
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| Alshaaer, Mazen | Brussels |
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| Bih, L. |
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| Casati, R. |
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| Muller, Hermance |
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| Kočí, Jan | Prague |
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| Šuljagić, Marija |
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| Kalteremidou, Kalliopi-Artemi | Brussels |
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| Azam, Siraj |
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| Ospanova, Alyiya |
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| Blanpain, Bart |
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| Ali, M. A. |
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| Popa, V. |
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| Rančić, M. |
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| Ollier, Nadège |
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| Azevedo, Nuno Monteiro |
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| Landes, Michael |
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| Rignanese, Gian-Marco |
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Timco, Grigore A.
in Cooperation with on an Cooperation-Score of 37%
Topics
Publications (12/12 displayed)
- 2024Two‐ and Three‐Spin Hybrid Inorganic‐Organic [2]Rotaxanes Containing Metallated Salen Groups
- 2020Heterometallic 3d-4f complexes as air-stable molecular pre-cursors in low temperature syntheses of stoichiometric rare-earth orthoferrite powderscitations
- 2018The synthesis of a monodisperse quaternary ferrite (FeCoCrO4) from the hot injection thermolysis of the single source precursor [CrCoFeO(O2C: TBu)6(HO2CtBu)3]citations
- 2018The synthesis of a monodisperse quaternary ferrite (FeCoCrO 4 ) from the hot injection thermolysis of the single source precursor [CrCoFeO(O 2 C : T Bu) 6 (HO 2 C t Bu) 3 ]citations
- 2017Portraying entanglement between molecular qubits with four-dimensional inelastic neutron scatteringcitations
- 2014A one-pot synthesis of monodispersed iron cobalt oxide and iron manganese oxide nanoparticles from bimetallic pivalate clusterscitations
- 2014Metal distribution and disorder in the crystal structure of [NH2Et2][Cr7MF8(tBuCO2)16] wheel molecules for M = Mn, Fe, Co, Ni, Cu, Zn and Cdcitations
- 2013Pressure versus temperature effects on intramolecular electron transfer in mixed-valence complexescitations
- 2013Synthesis of monodispersed magnetite nanoparticles from iron pivalate clusterscitations
- 2009Functional chromium wheel-based hybrid organic - Inorganic materials for dielectric applicationscitations
- 2009Experimental charge density in an oxidized trinuclear iron complex using 15 K synchrotron and 100 K conventional single-crystal X-ray diffractioncitations
- 2007Isolated heterometallic Cr7Ni rings grafted on Au(111) surfacecitations
Places of action
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article
Pressure versus temperature effects on intramolecular electron transfer in mixed-valence complexes
Abstract
Mixed-valence trinuclear carboxylates, [M 3 O(O 2 CR) 6 L 3 ] (M=metal, L=terminal ligand), have small differences in potential energy between the configurations M II M III M III ⇔ M III M II M III ⇔M III M III M II , which means that small external changes can have large structural effects, owing to the differences in coordination geometry between M 2+ and M 3+ sites (e.g., about 0.2 Å for Fe-O bond lengths). It is well-established that the electron transfer (ET) between the metal sites in these mixed-valence molecules is strongly dependent on temperature and on the specific crystal environment; however, herein, for the first time, we examine the effect of pressure on the electron transfer. Based on single-crystal X-ray diffraction data that were measured at 15, 90, 100, 110, 130, 160, and 298 K on three different crystals, we first unexpectedly found that our batch of Fe 3 O (O 2 CC(CH 3 ) 3 ) 6 (C 5 H 5 N) 3 (1) exhibited a different temperature dependence of the ET process than previous studies of compound 1 have shown. We observed a phase transition at around 130 K that was related to complete valence trapping and Hirshfeld surface analysis revealed that this phase transition was governed by a subtle competition between C-H⋯pi; and π⋯pi; intermolecular interactions. Subsequent high-pressure single-crystal X-ray diffraction at pressures of 0.15, 0.35, 0.45, 0.74, and 0.96 GPa revealed that it was not possible to trigger the phase transition (i.e., valence trapping) by a reduction of the unit-cell volume, owing to this external pressure. We conclude that modulation of the ET process requires anisotropic changes in the intermolecular interactions, which occur when various directional chemical bonds are affected differently by changes in temperature, but not by the application of pressure.