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Fernando Ruipérez

Fernando Ruipérez
Basque Center for Macromolecular Design and Engineering - POLYMAT Fundazioa

PhD Chemistry

About

103
Publications
18,595
Reads
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3,442
Citations
Additional affiliations
July 2013 - present
Polymat, University of the Basque Country (UPV/EHU) Spain
Position
  • Research Associate
January 2013 - June 2013
Donostia International Physics Center
Position
  • Visiting researcher
August 2010 - December 2012
University of the Basque Country
Position
  • PostDoc Position

Publications

Publications (103)
Article
Full-text available
The performance of waterborne (meth)acrylic coatings is critically affected by the film formation process, in which the individual polymer particles must join to form a continuous film. Consequently, the waterborne polymers present lower performance than their solvent-borne counter-polymers. To decrease this effect, in this work, ionic complexation...
Article
Full-text available
In recent years, responsive materials including dynamic bonds have been widely acclaimeddue to their expectation to pilot advanced materials. Within these materials, synthetic polymershave shown to be good candidates. Recently, the so-called frustrated Lewis pairs (FLP) have beenused to create responsive materials. Concretely, the activation of die...
Article
Photoinduced polymerization is a useful tool in many industrial applications such as coatings, adhesives and 3D printing. However, the use of light to promote polymerization has been almost exclusively used...
Article
Chemical recycling of plastic waste represents a greener alternative to landfill and incineration, and potentially offers a solution to the environmental consequences of increased plastic waste. Most plastics that are widely used today are designed for durability, hence currently available depolymerisation methods typically require harsh conditions...
Article
Herein, we demonstrate 3D printing of an elastomeric imidazolium polyamide-ionene which exhibits intrinsic shape-memory (SM) and self-healing (SH) character, reporting optimized printing conditions and rheological properties. This study shows the suitability of this material for 3D-printing via fused deposition modeling. The 3D-printed objects reta...
Article
Organic redox-active materials are actively being searched as a more sustainable alternative to traditional inorganic cathodes used in rechargeable batteries. Among the different types of organic cathodes, redox polymers based...
Article
The organocatalytic coupling of oxetanes and carbon dioxide (CO2) offers a sustainable route to poly(trimethylene carbonate)s and/or functional six-membered cyclic carbonate monomers. This transformation is more challenging than when using more strained epoxide comonomers and even more so when it is performed using metal-free routes. Herein, we rep...
Article
Functionalized cyclic carbonates are attractive monomers for the synthesis of innovative polycarbonates or polyurethanes for various applications. Even though their synthesis has been intensively investigated, doing so in a sustainable and efficient manner remains a challenge. Herein, we propose an organocatalytic procedure based on the depolymeriz...
Article
The emulsion copolymerization between vinyl acetate (VAc) and vinyl alkoxysilanes is an interesting yet not well-understood process. In the present work, the copolymerization between VAc and vinyl trimethoxysilane (VTMS) is taken as a model system and studied using different polymerization techniques in order to understand the underlying mechanism...
Article
Full-text available
Recently, it has been shown that the reaction mechanism in self-healing diphenyl dichalcogenide-based polymers involves the formation of sulfenyl and selenyl radicals. These radicals are able to attack a neighbouring dichalcogenide bond via a three-membered transition state, leading to the interchange of chalcogen atoms. Hence, the chain mobility i...
Article
The rapid development of computational hardware and software, as well as the advances in new theoretical methodologies have allowed quantum chemistry, in particular density functional theory, to become a fundamental tool in polymer science to predict, rationalise, develop and characterise polymeric materials. Quantum chemistry is able to provide in...
Article
A conducting redox polymer based on PEDOT with hydroquinone and pyridine pendant groups is reported and characterized as a proton trap material. The proton trap functionality, where protons are transferred from the hydroquinone to the pyridine sites, allows for utilization of the inherently high redox potential of the hydroquinone pendant group (3....
Article
A series of alkylated or protonated bicyclic amidine or DBU organocatalysts were investigated for the synthesis of cyclic carbonates from CO2 and epoxides. The impact of the counter anion was examined in protonated samples where salts featuring halides displayed superior activity as a consequence of the nucleophilicity of the halide. The simple iod...
Article
We have studied how cyclic topology affects the crystallization and morphology of π-conjugated poly(3-hexylthiophene) (P3HT) molecules by comparing linear and cyclic analogues for the first time, with three different chain lengths. We employ a range of experimental techniques including wide-angle X-ray scattering (WAXS), polarized light optical mic...
Article
A cobalt-catalyzed cyclotrimerization of bis(aryl)alkyne is used as an innovative tool to obtain hole-transport materials (HTMs). The novel HTM containing six units of oligotriarylamine (HAB1), characterized by UV−vis, cyclic voltammetry, DFT, and thermogravimetric analysis, confirms its suitability as an efficient HTM in PSCs. A PCE of 17.5% was o...
Article
In this work, theoretical methods of quantum chemistry are employed to estimate the effects that the structural modification of 1,5- and 9,10-anthraquinone molecules might produce in their electronic structure, in the pursuit of a common strategy to improve the electrochemical and singlet fission features of conjugated quinones. The proposed modifi...
Article
Full-text available
Self-healing materials are a very promising kind of materials due to their capacity to repair themselves. Among others, dichalcogenide-based materials are being widely studied due to their dynamic covalent bond nature. Recently, the reaction mechanism occurring in these materials was characterized both theoretically and experimentally. In this vein...
Preprint
Self-healing materials are a very promising kind of materials due to their capacity to repair themselves. Among others, dichalcogenide-based materials are being widely studied due to their dynamic covalent bond nature. Recently, the reaction mechanism occurring in these materials was characterized both theoretically and experimentally. In this vein...
Article
The polymerization of n-butyl acrylate (BA) and n-butyl methacrylate (BMA) in the presence of different amounts of a macromonomer containing vinyl aromatic terminal double bonds presents completely different behaviors. While the polymerization rate of BMA is not affected by increasing amounts of the macromonomer in the formulation (up to 40 wt%), t...
Article
The alkoxyamine 3-(((2-cyanopropan-2-yl)oxy)(cyclohexyl)amino)-2,2-dimethyl-3-phenyl-propanenitrile (Dispolreg 007) has recently emerged as a robust regulator for the controlled (co)polymerization of methacrylates and styrene by nitroxide mediated polymerization. However, whilst the successful use of this alkoxyamine in a number of systems has now...
Article
We report an investigation of a series of auropolyynes, Au-(C≡C) n -Au- (n = 1-3), using high-resolution photoelectron imaging and ab initio calculations. Vibrationally resolved photoelectron spectra are obtained, allowing the electron affinities of Au-(C≡C) n -Au to be accurately measured as 1.651(1), 1.715(1), and 1.873(1) eV for n = 1-3, respe...
Article
The emission of a bright blue fluorescence is a unique feature common to the vast variety of polymer carbon dots (CDs) prepared from carboxylic acid and amine precursors. However, the difficulty to assign a precise chemical structure to this class of CDs yet hampers the comprehension of their underlying luminescence principle. In this work, we show...
Article
The geometrical and electronic structures of 44 squarate and croconate derivatives are computationally studied in this work using theoretical methods of quantum chemistry, in the pursuit of new singlet fission sensitizers. Non‐negligible singlet open‐shell diradical character is observed for most of the studied molecules, which can be controlled th...
Article
Processability and recyclability of thermoset materials is a current challenge and a focus of intense research. Here we present a reprocessable and recyclable crosslinked poly (urea-urethane) vitrimer elastomer containing aromatic ureas and amines on its structure. A dynamic amine/urea exchange controlled by an associative mechanism is proposed in...
Article
Full-text available
Here we report for the first time an efficient fullerene‐based compound, FU7, able to act as Hole‐Transporting Material (HTM) and electron blocking contact. It has been applied on perovskite solar cells (PSCs), obtaining 0.81 times the efficiency of PSCs with the standard HTM, spiro‐OMeTAD, with the additional advantage that this performance is rea...
Article
Full-text available
The theoretical self‐healing capacity of new sulfenamide‐based disulfides is estimated by using theoretical methods of quantum chemistry. Starting from previously studied aromatic disulfides, the influence of inserting a NH group between the disulfide and the phenyl ring (forming the sulfenamide), as well as the role of the phenyl ring in the self‐...
Article
The world’s plastic production is continuously and exponentially increasing, creating millions of tons of short-lived items that end as waste and accumulate in the environment. Poly(ethylene terephthalate) (PET) provides one of the best examples as it is a non-biodegradable polymer that is mainly used as raw material for a wide range of packaging a...
Article
The electronic structure of 206 carbonyls and methylene derivatives based on conjugated cyclic hydrocarbons are computationally studied in this work using theoretical methods of quantum chemistry. The singlet open-shell nature of the ground state and its influence in the low-lying excited states is analyzed for 90 carbonyl (quinone, Q), 90 methylen...
Article
Molecular systems where two simple π-electron species, acetylene and ethylene, are linked by a cation located between them are analyzed in this study. In particular, the C2H2***M+***C2H2, C2H4***M+***C2H2 and C2H4***M+***C2H4 complexes (M+ = H+, Li+ and Au+) are calculated with the use of MP2 and CASPT2 methods. The Quantum Theory of Atoms in Molec...
Article
In this work, a theoretical protocol based on classical molecular dynamics has been defined, in order to study weak non-covalent interactions in diphenyl disulfide based compounds. This protocol is then used to study the influence of hydrogen bonds and π-π stacking in four selected cases, namely, the monosubstituted and amine ortho trisubstituted u...
Article
Dynamic structures containing polymers are considered a new class of polymeric materials with very attractive properties, since they can behave as thermosets at room temperature but at the same time they can be reprocessed to any shape. Recently, aromatic disulfides have been explored as dynamic bonds because of their good exchange reaction rate at...
Article
Full-text available
In the present work, a set of 90 conjugated carbonyls based on cyclic hydrocarbons with different ring sizes are studied by means of theoretical methods of quantum chemistry in order to analyze their singlet open-shell diradical character and its influence in different molecular properties. In particular, we have investigated the molecular structur...
Article
The design of high performance solid sorbent materials for CO2 capture is one of the searched technologies to mitigate global warming. However, the covalent incorporation of functionalities into polymeric supports usually involves multi-step energy-intensive chemical processes. This fact makes the net CO2 balance of the materials negative even thou...
Article
We report a joint photoelectron spectroscopy and theoretical study on AuC4 −, AuC6 −, and AuCnH− (n = 2, 4, and 6) using high-resolution photoelectron imaging and ab initio calculations. The ground state of AuC2H−, AuC4H−, and AuC6H− is found to be linear, while that of AuC4 − and AuC6 − is bent. All the species are found to be linear in their neut...
Article
In a recent publication, Nakamura and co-workers studied the termination mechanism in the radical polymerization of acrylates. Contrary to conventional thinking, their conclusion is that termination is overwhelmingly by disproportionation. This finding impacts on a large body of the previous work in the polymerization of acrylic monomers which this...
Article
Reduction of anthropogenic CO2 emissions and CO2 separation from post-combustion flue gases are among the imperative issues in the spotlight at present. Hence, it is highly desirable to develop efficient adsorbents for mitigating climate change with possible energy savings. Here, we report the design of a facile one pot catalyst-free synthetic prot...
Article
A quantum chemical study of the H2 activation at fluorides of coinage metals, MF (M = Cu, Ag and Au), and its splitting was performed. The following reaction path was analyzed: FM•••H2 → FH•••HM → HM•••FH, where both the molecular complexes and the corresponding transition states have been characterized at the CCSD(T)/aug-cc-pVQZ//MP2/aug-cc-pVQZ l...
Article
Reduction of anthropogenic CO 2 emissions and CO 2 separation from post-combustion flue gases are among the imperative issues in the spotlight at present. Hence, it is highly desirable to develop efficient adsorbents for mitigating climate change with possible energy savings. Here, we report the design of a facile one pot catalyst-free synthetic pr...
Article
The evaluation of four high-level composite methods based on the modification of Gaussian-3 (G3) theory for radicals and 18 exchange-correlation density functionals, including modern long-range and dispersion-corrected functionals, in the modelization of singlet diradicals has been performed in this work. Structural parameters and properties such a...
Article
The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are...
Article
There is a growing interest to develop green synthetic pathways towards industrially relevant polymers such as polyurethanes without the use of toxic and dangereous isocyanate monomers. The most promising route towards non-isocianete polyurethanes (NIPUs) is the aminolysis of dicyclic carbonates derived from renewable resources. Although, cyclic ca...
Article
Full-text available
4-Aminophenyl disulfide (4-AFD) has been recently reported as a hardener for the design of reprocessable, repairable and recyclable epoxy networks. Now we show that such a hardener is also responsible for a mechanochromic effect, due to an intermediate radical species formed upon damage, as confirmed by theoretical studies.
Article
Full-text available
Self-healing materials are a very promising kind of materials due to their capacity to repair themselves. Among others, diphenyl disulfide-based compounds (Ph2S2) appear to be among the best candidates to develop materials with optimum self-healing properties. However, few is known regarding both the reaction mechanism and the electronic structure...
Article
Aromaticity Study The lowest lying singlet, triplet, and quintet spin states of D3h Al{{{\minus \hfill \atop 3\hfill}}} have strong multireference character, which impedes the straightforward application of the Hückel-Baird-like electron counting rules based on the inspection of the molecular orbitals. However, electron delocalization can be assess...
Article
Full-text available
Radical formation through homolytic X-H bond cleavage in LiH, BH, CH4, NH3, H2O and HF is investigated using natural orbital functional theory in its recent PNOF6 implementation, which includes inter electron-pair correlation, and the results compared to PNOF5 level of theory, CASSCF wavefunction methods and experimental data. It is observed that P...
Article
Multiconfigurational high-level electronic structure calculations show that the ring-like cluster anion has three close low-lying electronic states of different spin, all of them having strong multiconfigurational character. The aromaticity of the cluster has, therefore, been studied by means of total electron delocalization and normalized multicen...
Article
Full-text available
Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization has emerged as one of the most versatile reversible deactivation radical polymerization techniques and is capable of polymerizing a wide range of monomers under various conditions. One of the most important factors governing the success of a RAFT polymerization is the fraction o...
Article
Full-text available
The ring-opening polymerization (ROP) of ethylene brassylate, catalyzed by the cyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is reported. Several experimental parameters were evaluated for bulk ROP process and polyesters, resulting in molecular weights between 3 and 15 kg mol−1. End-group analysis by 1H nuclear magnetic resonnance (NMR...
Article
The use of organocatalysts for the polymerization of ethylene brassylate, a commercially available, cheap, and renewable macro(di)lactone is reported for the first time. Ethylene brassylate was polymerized by ring-opening polymerization under bulk and solution conditions at 80 degrees C. Polymerizations were carried out in the presence of several o...
Article
Full-text available
In a recent paper (J. Chem. Phys. 139, 064111, 2013), an antisymmetrised product of strongly orthogonal geminals with the expansion coefficients explicitly expressed by means of the occupation numbers was used to generate the Piris natural orbital functional 5 (PNOF5). This functional describes most of the non-dynamical effects, but also an importa...
Article
Full-text available
The increased availability of aluminium in biological environments, due to human intervention in the last century, raises concerns on the effects that this so far "excluded from biology" metal might have on living organisms. Consequently, the bioinorganic chemistry of aluminium has emerged as a very active field of research. This review will focus...
Article
Intramolecular chain transfer to polymer and subsequent propagation of tertiary radicals cause extensive branching in radical polymerization of acrylic monomers. Studies in the literature have shown that under controlled radical polymerization conditions the extent of branching is significantly reduced. There are two competing theories to explain t...
Article
A theoretical investigation using density functional theory (DFT) has been carried out in order to understand the molecular mechanism of dihydrogen activation by means of transition metal dioxides MO2 (M = Ti, Zr and Hf), according to the following reaction: MO2 + H2 → MO + H2O. B3LYP/6-311++G(2df,2pd)/SDD methodology was employed considering two p...
Article
The study of the reactions of water and hydrogen sulfide with palladium and platinum cations has been completed in this work, in both low- and high-spin states. Our calculations predict that only the formation of platinum sulfide is exothermic (in both spin states), whereas for the remaining species the oxides and sulfides are found to be more reac...
Article
Full-text available
The natural orbital functional theory admits two unique representations in the orbital space. On the one hand, we have the natural orbitals themselves that minimize the energy functional, and which afford for a diagonal one-particle reduced density matrix but not for a diagonal Lagrangian orbital energy multipliers matrix. On the other hand, since...
Article
Full-text available
The optical spectrum of diatomic IrSi has been investigated for the first time, with transitions observed in the range from 17 178 to 23 858 cm(-1) (582-419 nm). A rich spectrum has been recorded, consisting of 14 electronic band systems and a number of unclassified bands. Thirty-one bands have been investigated with rotational resolution, allowing...
Article
The structural and energetic parameters of MU heterobimetallic dimers (M = Cr, Mo, W) have been computed using the complete active space self-consistent-field method followed by second-order perturbation theory. Our results show that the effective bond order (EBO) of the MoU dimer (5.5) is higher than that for the tungsten dimer (5.2), known to dat...
Article
Full-text available
In this paper, we present for the first time a description based on the natural orbital functional theory (NOFT) of the group VI dimers, namely, Cr2, Mo2 and W2. The PNOF5, Piris Natural Orbital Functional, has been used throughout this work, and the results are compared to multireferential perturbation theory (CASPT2) results. Both methods have be...
Article
Full-text available
The activation of methane and its subsequent conversion into more valuable feedstocks under ambient conditions are regarded as one of the major challenges in contemporary catalysis, due to its thermodynamically strong and kinetically inert C-H bond. Several enzymes and synthetic bioinorganic systems perform the activation of C-H bonds in methane an...
Article
Full-text available
The third (PNOF3), fourth (PNOF4) and fifth (PNOF5) versions of the Piris natural orbital functional were used to characterize the beryllium dimer. The results obtained were compared to those gained afforded by CASSCF and CASPT2 as well as experimental data. The equilibrium distances (R e), dissociation energies (D e), effective bond orders (EBOs),...
Article
Full-text available
Radical formation through hydrogen abstraction and C–C and O–O homolytic bond cleavage from selected molecules is investigated by use of natural orbital functional theory in its PNOF5 natural orbital functional implementation, and the results are compared to high-level ab initio complete active space self-consistent field (CASSCF) and complete acti...
Article
Full-text available
The excited states of the gold dimer have been investigated using modern theoretical tools including the multiconfigurational exact molecular mean-field intermediate Hamiltonian Fock-space Coupled Cluster, X2Cmmf-IHFSCC, and the complete active space self-consistent field followed by second order perturbation theory, CASSCF/CASPT2. The computed opt...
Article
Full-text available
A detailed computational study on the reaction mechanisms of the thermal activation of methane by the bare complex [Ni(H)(OH)](+) has been conducted. The experimentally observed reaction features, i.e. the ligand exchange Ni(H) → Ni(CH(3)), the H/D scrambling between the incoming methane and the hydrido ligand of the nickel complex, the spectator-l...
Article
US2 and SUO molecules have been prepared by laser ablation of the solid materials and reaction of the elements during condensation in solid argon, which give the same absorptions as earlier U atom reactions with sulfur vapor and sulfur dioxide. The antisymmetric stretching mode of US2 shifts from 438.7 cm(-1) in solid argon to 442.3 cm(-1) in solid...
Article
Full-text available
The dissociation of diatomic molecules of the 14-electron isoelectronic series N(2), O(2)(2+), CO, CN(-) and NO(+) is examined using the Piris natural orbital functional. It is found that the method describes correctly the dissociation limit yielding an integer number of electrons on the dissociated atoms, in contrast to the fractional charges obta...
Article
Heteronuclear dimers like CrMo, CrW, MoW, VCr, VMo, VW, and their anions have been investigated by means of multiconfigurational quantum chemistry methods, using the complete active space self-consistent field followed by second-order perturbation theory, CASSCF/CASPT2. We explored in great detail several spectroscopic properties such as bond lengt...
Article
The pro-oxidant activity of aluminum, a nonredox metal, through superoxide formation is studied by theoretical methods, determining the ESR g-tensor values of O(2)(center dot-) with a variety of metals and the reaction energies for Al(3+) superoxide affinity in solution. First, the intrinsic ability of aluminum to induce a splitting of the pi(g) le...
Article
Natural orbital functional theory (NOFT) in its PNOF3 and PNOF4 implementations is used to investigate the potential energy surface (PES) of ethylene torsion. This rearrangement is taken as a case study to illustrate the satisfactory performance of the Piris Natural Orbital Functional (PNOF) toward rearrangements sensible to non-dynamical electron...
Article
In this paper, we calculate the potential energy surface (PES) and the spectroscopic constants of the chromium dimer using the recently developed restricted active space second-order perturbation (RASPT2) method. This approach is benchmarked against available experimental measurements and the complete active space second-order perturbation theory (...