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1.
Modulation of charge transfer exciton dynamics in organic semiconductors using different structural arrangements
Cristian Soncini, Abhishek Kumar, Federica Bondino, Elena Magnano, Matija Stupar, Barbara Ressel, Giovanni De Ninno, Antonis Papadopoulos, Efthymis Serpetzoglou, Emmanuel Stratakis, Maddalena Pedio, 2023, original scientific article

Abstract: In devices based on organic semiconductors, aggregation and inter-molecular interactions play a key role in affecting the photo-physical and dynamical carrier properties of the material, potentially becoming a limiting factor to achieving high efficiency. As a consequence, a detailed understanding of the interplay between the film molecular structure and the material properties is essential to properly design devices with optimized performance. Here we demonstrate how different molecular structural arrangements modulate the charge transfer (CT) dynamics in cobalt phthalocyanine (CoPc) thin films. By transient absorption spectroscopy and time-resolved photoemission spectroscopy, we study the influence of different CoPc structures on the dynamical electronic properties, the CoPc intra and inter- molecular de-excitation pathways up to 7 ns. We rationalize the ultrafast formation of triplet states in the CoPc through an electron exchange process between the single-occupied Co3dz2 orbital and p orbitals of the macrocycle, which obviate for an energetically unfavourable spin-flip. We found enhanced CT exciton lifetime in the case of the herringbone structure with respect to the brickwork one, possibly explainable by a more efficient CT exciton delocalization along the stacking axis.
Keywords: charge transfer, organic molecules, time resolved spectroscopies
Published in RUNG: 30.06.2023; Views: 1205; Downloads: 4
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2.
3.
Introduction to Electronic Properties and Dynamics of Organic Complexes as Self‐Assembled Monolayers
Maddalena Pedio, 2017, independent scientific component part or a chapter in a monograph

Abstract: Self‐assembled monolayers (SAMs) of organic‐conjugated transition metal complexes on surfaces is a focus of both device engineering and basic science, since it is a key factor in nearly all important aspects of device performances, including operation voltages, degradation, and efficiency. The huge amount of literature results related to the first monolayer, and reorganization and self‐assembling processes are due to the general accepted result that structural and chemical properties of the first monolayer are the key parameters for controlled thin film growth. Optical and magneto‐electronic properties are intimately connected, and the accurate determination of electronic levels, excitation, and relaxation dynamics is mandatory for the optimization of electronic, photovoltaic, and opto‐electronic devices. Quite a number of electronic states is generated by the interaction of light with complex organic molecules. Time‐resolved spectroscopies are a new investigation tool that gives the possibility of correctly addressing their origin and life time. Examples of prototypical systems are presented and discussed. We review on complementary techniques, trying to single out how different approaches are fundamental to fully characterize these complex systems.
Keywords: self‐assembled monolayer (SAM), surface structures molecular layers, nanotechnology, electronic properties, spectroscopies, time resolved
Published in RUNG: 12.06.2017; Views: 4704; Downloads: 208
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4.
Structural phases of ordered FePc-nanochains self-assembled on Au(110)
Betti Maria Grazia, Pierluigi Gargiani, Carlo Mariani, Roberto Biagi, Jun Fujii, Giorgio Rossi, Andrea Resta, Stefano Fabris, Sara Fortuna, Xavier Torrelles, Manvendra Kumar, Maddalena Pedio, 2012, original scientific article

Abstract: Iron-phthalocyanine molecules deposited on the Au(110) reconstructed channels assemble into one-dimensional molecular chains, whose spatial distribution evolves into different structural phases at increasing molecular density. The plasticity of the Au channels first induces an ordered phase with a 5×5 symmetry, followed by a second long-range ordered structure composed by denser chains with a 5×7 periodicity with respect to the bare Au surface, as observed in the low-energy electron-diffraction (LEED) and grazing incidence X-ray diffraction (GIXRD) patterns. The geometry of the FePc molecular assemblies in the Au nanorails is determined by scanning tunneling microscopy (STM). For the 5×7 phases, the GIXRD analysis identifies a “4-3” rows profile along the [001] direction in the Au surface and an on-top FePc adsorption site, further confirmed by density functional theory (DFT) calculations. The latter also reveals the electronic mixing of the interface states. The chain assembly is driven by the molecule–molecule interaction and the chains interact with the Au nanorails via the central metal atom, while the chain–chain distance in the different structural phases is primarily driven by the plasticity of the Au surface.
Keywords: STM, LEED, DFT, density functional theory, phthalocyanine, Au(110), gold, surface
Published in RUNG: 13.10.2016; Views: 4885; Downloads: 0
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5.
Spin and orbital configuration of metal phthalocyanine chains assembled on the Au(110) surface
Gargiani Pierluigi, Giorgio Rossi, Roberto Biagi, Valdis Corradini, Maddalena Pedio, Sara Fortuna, Arrigo Calzolari, Stefano Fabris, Julio Criginski Cezar, N. B. Brookes, Maria Grazia Betti, 2013, original scientific article

Abstract: The spin and orbital configuration of magnetic metal phthalocyanines (MPcs) deposited on metallic substrates are strongly influenced by the rehybridization of the molecular states with the underlying metal. FePc, CoPc, and CuPc isolated molecules are archetypal systems to investigate the interrelationship between magnetic moments and orbital symmetry after deposition on a metallic substrate. MPcs form long-range ordered chains self-assembled along the reconstructed channels of the Au(110) surface. X-ray magnetic circular dichroism from the L2,3 absorption edges of Fe, Co, and Cu shows that the orbital and spin configuration are strongly modified upon adsorption on the Au(110) surface if the orbitals responsible of the magnetic moment are involved in the interaction process. The magnetic moment for a single layer of molecular chains is completely quenched for the CoPc molecules, fully preserved for the CuPc and reduced for the FePc ones. The modified magnetic configuration is confined to the very interface layer, i.e., to the MPc molecules bound to the metal substrate up to the compact packing of the single layer. The different response can be rationalized in terms of the symmetry/orientation of the metal-ion d states interacting with the substrate states, as indicated by density functional theory calculations in agreement with experimental findings.
Keywords: phthalocyanine, Au(110), gold, self-assembly, pattern, configuration, density functional theory, DFT, CuPc, FePc
Published in RUNG: 12.10.2016; Views: 4873; Downloads: 0
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