Reversible Fe Magnetic Moment Switching in Catalytic Oxygen Reduction Reaction of Fe-Phthalocyanine Adsorbed on Ag(110)

Bartolomé, J.; Bartolomé, Fernando; Brookes, N. B.; Sedona, Francesco; Basagni, Andrea; Forrer, Daniel; Sambi, Mauro

doi:10.1021/acs.jpcc.5b02916

Cited by 18 publications

(55 citation statements)

References 39 publications

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“…FePc has been the object of a huge number of L 2,3 -edges XAS studies [ 33 , 34 , 38 , 120 , 124 , 125 , 126 , 127 ]. Among them, Bartolomé et al [ 125 ] investigated the Fe magnetic moment switching in the catalytic ORR of FePc adsorbed on Ag(110) by combining the results of X-ray linear polarized absorption spectroscopy with those of X-ray magnetic circular dichroism at the Fe L 2,3 -edges. A detailed analysis of the || and ⊥ Fe L 2,3 -edges components of the FePc and FePc( η 2 -O 2 ) XA spectra has been recently reported by Carlotto et al [ 38 ] by adopting a computational set-up slightly different from that herein employed.…”

Section: Resultsmentioning

confidence: 99%

A Theoretical Study of the Occupied and Unoccupied Electronic Structure of High- and Intermediate-Spin Transition Metal Phthalocyaninato (Pc) Complexes: VPc, CrPc, MnPc, and FePc

et al. 2020

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The structural, electronic, and spectroscopic properties of high- and intermediate-spin transition metal phthalocyaninato complexes (MPc; M = V, Cr, Mn and Fe) have been theoretically investigated to look into the origin, symmetry and strength of the M–Pc bonding. DFT calculations coupled to the Ziegler’s extended transition state method and to an advanced charge density and bond order analysis allowed us to assess that the M–Pc bonding is dominated by σ interactions, with FePc having the strongest and most covalent M–Pc bond. According to experimental evidence, the lightest MPcs (VPc and CrPc) have a high-spin ground state (GS), while the MnPc and FePc GS spin is intermediate. Insights into the MPc unoccupied electronic structure have been gained by modelling M L2,3-edges X-ray absorption spectroscopy data from the literature through the exploitation of the current Density Functional Theory variant of the Restricted Open-Shell Configuration Interaction Singles (DFT/ROCIS) method. Besides the overall agreement between theory and experiment, the DFT/ROCIS results indicate that spectral features lying at the lowest excitation energies (EEs) are systematically generated by electronic states having the same GS spin multiplicity and involving M-based single electronic excitations; just as systematically, the L3-edge higher EE region of all the MPcs herein considered includes electronic states generated by metal-to-ligand-charge-transfer transitions involving the lowest-lying π* orbital (7eg) of the phthalocyaninato ligand.

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Section: Resultsmentioning

confidence: 99%

A Theoretical Study of the Occupied and Unoccupied Electronic Structure of High- and Intermediate-Spin Transition Metal Phthalocyaninato (Pc) Complexes: VPc, CrPc, MnPc, and FePc

et al. 2020

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“…The ability to modify the spin of a molecule in a controlled and reversible way is essential to develop novel spin-based technologies 1 . Although the spin of surface-supported single molecules is mainly determined by molecule/surface interactions 2 – 5 , it can be modified by external parameters such as the mechanical 6 or the chemical modification of the molecule 7 – 12 , the application of electric fields 13 – 15 , light or temperature 16 , 17 . The effect of approaching the metallic tip of a scanning tunneling microscope (STM) to the molecule is a way to alter the local environment of the molecule 18 , 19 .…”

Section: Introductionmentioning

confidence: 99%

Controlled spin switching in a metallocene molecular junction

et al. 2017

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The active control of a molecular spin represents one of the main challenges in molecular spintronics. Up to now spin manipulation has been achieved through the modification of the molecular structure either by chemical doping or by external stimuli. However, the spin of a molecule adsorbed on a surface depends primarily on the interaction between its localized orbitals and the electronic states of the substrate. Here we change the effective spin of a single molecule by modifying the molecule/metal interface in a controlled way using a low-temperature scanning tunneling microscope. A nickelocene molecule reversibly switches from a spin 1 to 1/2 when varying the electrode–electrode distance from tunnel to contact regime. This switching is experimentally evidenced by inelastic and elastic spin-flip mechanisms observed in reproducible conductance measurements and understood using first principle calculations. Our work demonstrates the active control over the spin state of single molecule devices through interface manipulation.

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“…Given the small size of molecules and relying on their chemical stability, a relatively high information density can be obtained with a potentially negligible energy consumption, provided that a reliable method is found to address each molecule individually for writing/ reading. [1][2][3][4][5][6][7] Porphyrins-heterocyclic compounds where four pyrrole units are arranged to form a macrocycle-are ideal candidates for this kind of application: the planar structure of the macrocycle and the possibility of tuning the chemical nature of the peripheral groups makes it possible to organize such molecules on flat substrates in an ordered fashion, 8 while the possibility of hosting a metallic ion at the center with unpaired 3d electrons ensures the presence of localized magnetic moments. 9,10 When chemical reactions occur within those molecules, specific molecular arrangements are induced and both the electronic and magnetic properties are significantly affected.…”

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confidence: 99%