Manuel Souto

University of Aveiro | UA · Division of Chemistry

Electroactive organic materials have received much attention as alternative electrodes for metal-ion batteries due to their tuneable electrochemical properties, high theoretical capacity, resources availability, and environmental friendliness. In particular, redox-active covalent organic frameworks (COFs) have recently emerged as promising electrod...

Covalent organic frameworks (COFs) are crystalline porous organic polymers that have recently emerged as promising electrode materials for rechargeable batteries. Herein, we present an approach to improve the electrochemical performance of an anthraquinone-based COF (DAAQ-TFP-COF) cathode material in metal anode (Li, Mg) based batteries through pro...

Invited for the cover of this issue is the group of Manuel Souto and co-workers at the University of Aveiro and CICECO-Aveiro Institute of Materials. The image depicts the direct C-H arylation of dithiophene-tetrathiafulvalene (DT-TTF) and the self-assembly of DT-TTF-tetrabenzoic acid studied by using scanning tunnelling microscopy. Read the full t...

The incorporation of electroactive organic building blocks into coordination polymers (CPs) and metal-organic frameworks (MOFs) offers a promising approach for adding electronic functionalities such as redox activity, electrical conductivity, and luminescence to these materials. The incorporation of perylene moieties into CPs is, in particular, of...

Tetrathiafulvalene is among the most well-known building blocks in molecular electronics due to its outstanding electron-donating and redox properties. Among its derivatives, dithiophene-tetrathiafulvalene (DT-TTF) has attracted considerable interest in organic electronics, owing to its high field-effect mobility. Herein, we report the direct C-H a...

The advent of new solid‐state energy storage devices to tackle the electrical revolution requires the usage of nonlinear behavior leading to emergent phenomena. The ferroelectric analyzed herein belongs to a family of electrolytes that allow energy harvesting and storage as part of its self‐charging features when thermally activated. The Na2.99Ba0....

Tetrathiafulvalene is among the most well-known building block in molecular electronics due to its outstanding electron-donating and redox properties. Among its derivatives, dithiophene-tetrathiafulvalene (DT-TTF) received a lot of interest for organic electronics due to its high charge mobility. Herein we report the direct C-H arylation of DT-TTF...

Electrically conductive Metal-Organic Frameworks (MOFs) have emerged in the past few years as promising materials towards applications in (opto)electronics, electrocatalysis and energy storage, among others. One of the most common...

The discovery of organic metals in the 1970s opened the door to the design of electrical devices based on traditionally inert (insulating) organic materials. More recently, demonstration of record-high charge mobility and unusual electronic structure (e.g. Dirac cones) in graphene have given rise to an entire new field of two-dimensional (2D) mater...

Herein, we describe how video games, TV shows, or movies have been used to provide an innovative framework for students to think about chemistry and chemical engineering. The main objective of this paper is to show how science can be linked with pop-culture, to provide educators with recent materials to use in classrooms, and to discuss the benefit...

A family of hexakis-substituted [60]fullerene adducts endowed with the well-known tridentate 2,6-bis(pyrazol-1-yl)pyridine (bpp) ligand for spin-crossover (SCO) systems has been designed and synthesized. It has been experimentally and theoretically demonstrated that these molecular scaffolds are able to form polynuclear SCO complexes in solution. U...

Electroactive organic molecules exhibiting electrical conductivity, redox‐activity, optical or magnetic properties have emerged in recent years as promising building blocks for the design of crystalline porous frameworks, such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), with numerous functions in electronics. In this...

Herein we report the formation and characterization of two novel Zn-based multifunctional metal-organic frameworks (MOFs) based on 1H-indazole-5-carboxylic acid and bipyridine-like linkers, synthesized by soft solvothermal routes. These materials possess isoreticular two-fold interpenetrated 3D-structures which afford a flexible character and allow...

Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the des...

The design of metal-organic frameworks (MOFs) incorporating electroactive guest molecules in the pores has become a subject of great interest in order to obtain additional electrical functionalities within the framework while maintaining porosity. Understanding the charge-transfer (CT) process between the framework and the guest molecules is a cruc...

Here we show for the first time a MOF that is photocatalytically active for the light-assisted CO2 methanation at mild conditions (215 °C) without the inclusion of metallic nanoparticles or...

div>Here we show for the first time a MOF that is photocatalytically active for the light-assisted CO₂ methanation at mild conditions (215 °C) without the inclusion of metallic nanoparticles or any sacrificial agent. The presence of Cu₂O nanoparticles causes a 50 % increase in the photocatalytic activity. These results pave...

Tetrathiafulvalene‐Lanthanide (TTF‐Ln) Metal‐Organic Frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein we report a new family of isostructural TTF‐Ln MOFs, denoted as MUV‐5(Ln) (Ln =...

div>Tetrathiafulvalene-Lanthanide (TTF-Ln) Metal-Organic Frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein we report a new family of isostructural TTF-Ln MOFs, denoted as MUV-5(Ln) (L...

p>The design of Metal-Organic Frameworks (MOFs) incorporating electroactive guest molecules in the pores has become a subject of great interest in order to install additional electrical functionalities within the framework while maintaining porosity. In this direction, understanding the charge-transfer (CT) process between the framework and the gue...

We describe the modification of the Work Function (WF) of Au(111) upon deposition of Self-Assembled Monolayers (SAMs) with two donor-acceptor (D-A) systems, one based on a ferrocene-polychlorotriphenylmethyl radical (Fc-PTM) dyad and another on its non-radical dyad analogue. Kelvin Probe Force Microscopy (KPFM) has been used to measure the changes...

The electron donor-acceptor tetrathiafulvalene-polychlorotriphenylmethyl (PTM) radical dyad, which shows a strong interplay between intra- and intermolecular charge transfer processes in solution, has been deposited by drop-casting on highly oriented pyrolytic graphite substrates, and its self-assembled structure has been investigated. Conducting a...

The crystal structure of an interpenetrated tetrathiafulvalene(TTF)-based metal-organic framework (MOF) is reported. This MOF, denoted MUV-2-i, is the interpenetrated analogue of the hierarchical and flexible MUV-2. Interestingly, the large flexibility exhibited by MUV-2 upon polar solvent adsorption is considerably reduced in the interpenetrated f...

p>The crystal structure of an interpenetrated tetrathiafulvalene(TTF)- based metal-organic framework (MOF) is reported. This MOF, denoted MUV-2-i, is the interpenetrated analogue of the hierarchical and flexible MUV-2. Interestingly, the large flexibility exhibited by MUV-2 upon polar solvent adsorption is considerably reduced in the interpenetrate...

Charge injection barriers at metal/organic interfaces can be tuned by modifying the work function of metallic electrodes using self‐assembled monolayers (SAMs) of polar molecules. An interesting example of polar molecules is offered by donor–acceptor (D–A) dyads based on ferrocene (Fc) as electron‐donor unit and either a polychlorotriphenylmethyl r...

Dyads formed by an electron donor unit (D) covalently linked to an electron acceptor (A) by an organic bridge are promising materials as molecular rectifiers. Very recently, we have reported the charge transport measurements across self-assembled monolayers (SAMs) of two D-A systems consisting of the ferrocene (Fc) electron-donor linked to a polych...

“Breathing” metal-organic frameworks (MOFs) exhibiting changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multi-functional “breathing” frameworks. Here...

Single-component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalised planar radicals, we present here a nonplanar and spin localised radical...

Herein we report the synthesis of a tetrathiafulvalene (TTF)-based MOF, namely MUV-2, which shows a non-interpenetrated hierarchical crystal structure with mesoporous one-dimensional channels of ca. 3 nm and orthogonal microporous channels of ca. 1 nm. This highly stable MOF (aqueous solution with pH values ranging 2-11 and different organic solven...

Organic ferroelectric materials operating at room temperature are in demand in the emerging field of lightweight, flexible and environmentally friendly electronics. Tayi et al.1 reported room-temperature ferroelectricity in organic mixed-stack charge-transfer crystals, produced using a supramolecular design concept—the lock-arm supramolecular order...

In this article, three conjugated donor-Π-acceptor radical systems (1a-1c) based on a tetrathiafulvalene (TTF) unit, as electron-donor, connected to a polychlorotriphenylmethyl (PTM) radical, as electron-acceptor, through different vinylene units as bridge have been synthesized. The dependence of the intramolecular charge transfer on the length of...

This article describes the mechanism of charge transport across self-assembled monolayers (SAMs) of two donor-acceptor (D-A) systems consisting of polychlotriphenylmethyl (PTM) electron-acceptor moiety linked to an electron-donor ferrocene (Fc) unit supported by ultraflat template-stripped Au (AuTS) and contacted by eutectic alloy of gallium and in...

Organic donor–acceptor (D–A) systems formed by the electron-donor tetrathiafulvalene (TTF) linked to the electron-acceptor perchlorotriphenylmethyl (PTM) radical through different π-conjugated bridges exhibit interesting physical properties such as bistability in solution or conductivity in solid state. Understanding the interplay between intra- an...

During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF) unit by a π-conjugated bridge (1) that behaves as a s...

The understanding of the crystal structure of organic compounds, and its relationship to their physical properties, have become essential to design new advanced molecular materials. In this context, we present a computational study devoted to rationalize the different crystal packing displayed by two closely-related organic systems based on the TTF...

During the last years there has been a high interest in the development of new purely-organic single-component conductors. Very recently, we have reported a new neutral radical conductor based on the perchlorotriphenylmethyl (PTM) radical moiety linked to a monopyrrolo-tetrathiafulvalene (MPTTF) unit by a -conjugated bridge (1). Interestingly, thi...

This Thesis is focused on the design, synthesis and characterization of new multifunctional molecular materials based on donor-acceptor (D-A) dyads formed by the electron-donor tetrathiafulvalene (TTF) unit linked to the electron-acceptor polychlorotriphenylmethyl (PTM) radical moiety through different -conjugated bridges. These compounds can exhi...

The diradical acceptor-donor-acceptor triad 1··, based on two polychlorotriphenylmethyl (PTM) radicals connected through a tetrathiafulvalene(TTF)-vinylene bridge, has been synthesized. The generation of the mixed-valence radical anion, 1·-, and triradical cation species, 1···+, obtained upon electrochemical reduction and oxidation, respectively, w...

An electron donor-acceptor dyad based on a polychlorotriphenylmethyl (PTM) radical subunit linked to a tetrathiafulvalene (TTF) unit through a π-conjugated N-phenyl-pyrrole-vinylene bridge has been synthesized and characterized. The intramolecular electron transfer process and magnetic properties of the radical dyad have been evaluated by cyclic vo...

A comparative analysis of the physicochemical properties of different donor–acceptor dyads, based on a perchlorotriphenylmethyl radical acceptor subunit linked through a vinylene π-bridge to ferrocene derivatives (1–3) or a tetrathiafulvalene (4) donor subunit, is presented. Intramolecular electron transfer and charge delocalization of these donor–...

The electron donor–acceptor dyad 1, based on a polychlorotriphenylmethyl radical subunit linked to a tetrathiafulvalene moiety, shows in DMF solution a reversible temperature-induced switching between diamagnetic dimers, observed at room temperature, and paramagnetic monomers at high temperature. Different optical and magnetic properties are observ...

An extensive investigation of aggregation phenomena occurring in solution for a family of electron donor–acceptor derivatives, based on polychlorotriphenylmethyl radicals (PTM) linked via a vinylene-bridge to tetrathiafulvalene (TTF) units, is presented. A large set of temperature and/or concentration dependent optical absorption and electron spin...

Bistability of valence tautomeric donor–acceptor dyads formed by covalently linking a ferrocene-based electron-donor and the perchlorotriphenylmethyl radical, as the electron-acceptor, is tuned via a chemical modification of the ferrocene group. Specifically, the methylation of the ferrocene unit increases the strength of the donor group stabilizin...

An organic switch: An open-shell dyad, consisting of an electron acceptor perchlorotriphenylmethyl radical unit linked to an electron π-donor tetrathiafulvalene unit through a vinylene π-bridge, was synthesized. The self-assembly of the dyad in solution induced by its intramolecular electron transfer was studied.