Dynamic covalent urea bonds and their potential for development of self-healing polymer materials

2019

Self-healing polymer materials have drawn rapidly increasing interest over the last decade, and have been studied and used in an ever-increasing range of applications. Herein, we successfully make the covalent urea bond – a pinnacle of stability due to strong resonance effects – dynamic in nature through mediation of zinc salts. The dynamic covalent character of urea in the presence of zinc ions is confirmed through dissociation reaction experiments and quantum chemical calculations of small-molecule model urea compounds. In line with our experiments, the modelling results suggest that the presence of zinc ions speeds up the reaction of urea dissociation by two orders of magnitude via the f…

Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies

2018

Stimulated by its success in both bioconjugation and surface modification, we studied the strain-promoted oxidation-controlled cycloalkyne–1,2-quinone cycloaddition (SPOCQ) in three ways. First, the second-order rate constants and activation parameters (ΔH⧧) were determined of various cyclooctynes reacting with 4-tert-butyl-1,2-quinone in a SPOCQ reaction, yielding values for ΔH⧧ of 4.5, 7.3, and 12.1 kcal/mol, for bicyclo[6.1.0]non-4-yne (BCN), cyclooctyne (OCT), and dibenzoazacyclooctyne (DIBAC), respectively. Second, their reaction paths were investigated in detail by a range of quantum mechanical calculations. Single-configuration theoretical methods, like various DFT and a range of MP2…

Proton conductivity through polybenzimidazole composite membranes containing silica nanofiber mats

2019

The quest for sustainable and more efficient energy-converting devices has been the focus of researchers&prime

Rapid and Complete Surface Modification with Strain-Promoted Oxidation-Controlled Cyclooctyne-1,2-Quinone Cycloaddition (SPOCQ)

2017

Abstract Strain‐promoted oxidation‐controlled cyclooctyne‐1,2‐quinone cycloaddition (SPOCQ) between functionalized bicyclo[6.1.0]non‐4‐yne (BCN) and surface‐bound quinones revealed an unprecedented 100 % conjugation efficiency. In addition, monitoring by direct analysis in real time mass spectrometry (DART‐MS) revealed the underlying kinetics and activation parameters of this immobilization process in dependence on its microenvironment.

A Deep Insight into Different Acidic Additives as Doping Agents for Enhancing Proton Conductivity on Polybenzimidazole Membranes

2020

[EN] The use of phosphoric acid doped polybenzimidazole (PBI) membranes for fuel cell applications has been extensively studied in the past decades. In this article, we present a systematic study of the physicochemical properties and proton conductivity of PBI membranes doped with the commonly used phosphoric acid at different concentrations (0.1, 1, and 14 M), and with other alternative acids such as phytic acid (0.075 M) and phosphotungstic acid (HPW, 0.1 M). The use of these three acids was reflected in the formation of channels in the polymeric network as observed by cross-section SEM images. The acid doping enhanced proton conductivity of PBI membranes and, after doping, these conducti…

Innentitelbild: Strain-Promoted Cycloaddition of Cyclopropenes with o -Quinones: A Rapid Click Reaction (Angew. Chem. 32/2018)

2018

Diastereoselectivity of the Addition of Propargylic Magnesium Reagents to Fluorinated Aromatic Sulfinyl Imines.

2021

The addition of propargylmagnesium bromide to fluorinated aromatic sulfinyl imines gave homopropargyl amines with total regio- and diastereoselection. Complete reversal of diastereoselectivity can be achieved in some cases using coordinating (THF) or noncoordinating (DCM) solvents. Substituted propargylic magnesium reagents have been also tested toward fluorinated aryl sulfinyl imines affording chiral homoallenyl amines with good yields and selectivity control. DFT calculations helped to rationalize the origin of the experimental regio- and diastereoselectivities observed in each case.

Organic Monolayers by B(C6F5)3-Catalyzed Siloxanation of Oxidized Silicon Surfaces

2017

Inspired by the homogeneous catalyst tris(pentafluorophenyl) borane [B(C6F5)3], which acts as a promotor of Si-H bond activation, we developed and studied a method of modifying silicon oxide surfaces using hydrosilanes with B(C6F5)3 as the catalyst. This dedihydrosiloxanation reaction yields complete surface coverage within 10 min at room temperature. Organic monolayers derived from hydrosilanes with varying carbon chain lengths (C8-C18) were prepared on oxidized Si(111) surfaces, and the thermal and hydrolytic stabilities of the obtained monolayers were investigated in acidic (pH 3) medium, basic (pH 11) medium, phosphate-buffered saline (PBS), and deionized water (neutral conditions) for …

Acylsemicarbazide Moieties with Dynamic Reversibility and Multiple Hydrogen Bonding for Transparent, High Modulus, and Malleable Polymers

2020

The realization of covalent adaptable networks with excellent mechanical and dynamic properties remains a major challenge. Herein, the acylsemicarbazide (ASC) moieties with dynamic reversibility and multiple hydrogen bonding were disclosed and used to prepare transparent, high modulus, and malleable polymer networks. It was found that the ASC moiety can reversibly generate isocyanate and hydrazide at elevated temperatures, that is, exhibiting dynamic reversibility. ASC can also produce the disordered multiple hydrogen bonds that contribute to superior mechanical strength for dynamic polymers. The hydrogen bonding in ASC moieties can diminish the energy barrier for the cleavage of dynamic co…

Effect of metallacarborane salt H[COSANE] doping on the performance properties of polybenzimidazole membranes for high temperature PEMFCs

2020

[EN] In this paper, a series of composite proton exchange membranes comprising a cobaltacarborane protonated H[Co(C2B9H11)(2)] named (H[COSANE]) and polybenzimidazole (PBI) for a high temperature proton exchange membrane fuel cell (PEMFC) is reported, with the aim of enhancing the proton conductivity of PBI membranes doped with phosphoric acid. The effects of the anion [Co(C2B9H11)(2)] concentration in three different polymeric matrices based on the PBI structure, poly(2,2 '-(m-phenylene)-5,5 '-bibenzimidazole) (PBI-1), poly[2,2 '-(p-oxydiphenylene)-5,5 '-bibenzimidazole] (PBI-2) and poly(2,2 '-(p-hexafluoroisopropylidene)-5,5 '-bibenzimidazole) (PBI-3), have been investigated. The conducti…

Strain-Promoted Cycloaddition of Cyclopropenes with o-Quinones : A Rapid Click Reaction

2018

Abstract Novel click reactions are of continued interest in fields as diverse as bio‐conjugation, polymer science and surface chemistry. Qualification as a proper “click” reaction requires stringent criteria, including fast kinetics and high conversion, to be met. Herein, we report a novel strain‐promoted cycloaddition between cyclopropenes and o‐quinones in solution and on a surface. We demonstrate the “click character” of the reaction in solution and on surfaces for both monolayer and polymer brush functionalization.

Unveiling anion-induced folding in tripodal imidazolium receptors by ion-mobility mass spectrometry.

2021

The anion-induced folding of tripodal imidazolium receptors has been investigated by NMR spectroscopy, electrospray ionization ion mobility mass spectrometry and DFT calculations. Such folding can be switched by anion release upon collision induced dissociation.

Pauson–Khand reaction of fluorinated compounds

2020

The Pauson–Khand reaction (PKR) is one of the key methods for the construction of cyclopentenone derivatives, which can in turn undergo diverse chemical transformations to yield more complex biologically active molecules. Despite the increasing availability of fluorinated building blocks and methodologies to incorporate fluorine in compounds with biological interest, there have been few significant advances focused on the fluoro-Pauson–Khand reaction, both in the inter- and intramolecular versions. Furthermore, the use of vinyl fluorides as olefinic counterparts had been completely overlooked. In this review, we collect the advances both on the stoichiometric and catalytic intermolecular an…

The Ruthenium‐Catalyzed Domino Cross Enyne Metathesis/Ring‐Closing Metathesis in the Synthesis of Enantioenriched Nitrogen‐Containing Heterocycles

2020

Dual-Polarization Interferometry: A Novel Technique To Light up the Nanomolecular World

2015

[EN] The challenging lecture given in 1959 by physicist and Nobel Prize awarded R. P. Feynman: “There's plenty of room at the bottom” is considered to be the starting point for nanotechnology. With this peculiar title, Feynman encouraged researchers to explore beyond the atomic level and predicted exciting new phenomena that might revolutionize science and technology. Among these pioneering researchers are Eric Betzig, Stefan W. Hell and William E. Moerner, who have been awarded with the Nobel Prize in Chemistry 2014 for developing the super-resolved fluorescence microscopy. However, it is important to remark that the exploration of this amazing nanomolecular world began in the early 1980s …

Computational Study on the Co-Mediated Intramolecular Pauson–Khand Reaction of Fluorinated and Chiral N-Tethered 1,7-Enynes

2022

The Co2(CO)8-mediated intramolecular Pauson−Khand reaction is an elegant approach to obtain cyclopentenone derivatives containing asymmetric centers. In this work, we employed density functional theory calculations at the M11/6-311+G(d,p) level of theory to investigate the mechanism and reactivity for the Pauson−Khand reaction of fluorinated and asymmetric N-tethered 1,7-enynes. The rate determining step was found to be the intramolecular alkene insertion into the carbon−cobalt bond. The stereoselectivity of the alkene insertion step was rationalized by the different transition states showing the coordination of the alkene through the Re- and Si-face. The effects of different fluorine group…

Electric Conductivity Study of Porous Polyvinyl Alcohol/Graphene/Clay Aerogels: Effect of Compression.

2022

In this work, poly(vinyl alcohol) (PVOH)/graphene (GN) oxide/clay aerogels were prepared using montmorillonite (MMT) and kaolinite (KLT) as fillers. This work paves the way for the development of aerogels filled with MMT or KLT with high conductivity. The mechanical properties of the polymer/clay aerogels are enhanced by incorporating GN into these systems. These composite materials have an enhanced thermal stability, and the combination of PVOH and GN leads to interconnected channels which favored the conductivity when a clay (MMT or KLT) is added to the mixed PVOH/GN matrix. However, after compressing the samples, the conductivities drastically decreased. These results show that the desig…

Use of Ambient Ionization High-Resolution Mass Spectrometry for the Kinetic Analysis of Organic Surface Reactions

2016

In contrast to homogeneous systems, studying the kinetics of organic reactions on solid surfaces remains a difficult task due to the limited availability of appropriate analysis techniques that are general, high-throughput, and capable of offering quantitative, structural surface information. Here, we demonstrate how direct analysis in real time mass spectrometry (DART-MS) complies with above considerations and can be used for determining interfacial kinetic parameters. The presented approach is based on the use of a MS tag that - in principle - allows application to other reactions. To show the potential of DART-MS, we selected the widely applied strain-promoted alkyne-azide cycloaddition …

Rapid Surface Functionalization of Hydrogen-Terminated Silicon by Alkyl Silanols

2017

Surface functionalization of inorganic semiconductor substrates, particularly silicon, has focused attention toward many technologically important applications, involving photovoltaic energy, biosensing and catalysis. For such modification processes, oxide-free (H-terminated) silicon surfaces are highly required, and different chemical approaches have been described in the past decades. However, their reactivity is often poor, requiring long reaction times (2-18 h) or the use of UV light (10-30 min). Here, we report a simple and rapid surface functionalization for H-terminated Si(111) surfaces using alkyl silanols. This catalyst-free surface reaction is fast (15 min at room temperature) and…

Proton Exchange Membrane Fuel Cells (PEMFCs): Advances and Challenges

2021

The study of the electrochemical catalyst conversion of renewable electricity and carbon oxides into chemical fuels attracts a great deal of attention by different researchers. The main role of this process is in mitigating the worldwide energy crisis through a closed technological carbon cycle, where chemical fuels, such as hydrogen, are stored and reconverted to electricity via electrochemical reaction processes in fuel cells. The scientific community focuses its efforts on the development of high-performance polymeric membranes together with nanomaterials with high catalytic activity and stability in order to reduce the platinum group metal applied as a cathode to build stacks of proton …

Recent Progress in the Development of Composite Membranes Based on Polybenzimidazole for High Temperature Proton Exchange Membrane (PEM) Fuel Cell Ap…

2020

[EN] The rapid increasing of the population in combination with the emergence of new energy-consuming technologies has risen worldwide total energy consumption towards unprecedent values. Furthermore, fossil fuel reserves are running out very quickly and the polluting greenhouse gases emitted during their utilization need to be reduced. In this scenario, a few alternative energy sources have been proposed and, among these, proton exchange membrane (PEM) fuel cells are promising. Recently, polybenzimidazole-based polymers, featuring high chemical and thermal stability, in combination with fillers that can regulate the proton mobility, have attracted tremendous attention for their roles as PE…

Influence of the anion on diffusivity and mobility of ionic liquids composite polybenzimidazol membranes

2020

[EN] The study of proton conductivity processes has received increasing attention in the past decades due to their potential applications in fields such as electrochemical devices and fuel cells. Despite the high number of composite membranes which have been described for this purpose, fundamental studies of the conduction phenomena in polymeric membranes are scarce. In this article, we study on the effect of the anion on ionic conductivity of ionic liquid composite polybenzimidazole (PBI) membranes. These membranes, which contain 1-butyl-3-methylimidazolium (BMIM) with different counterions ([Cl]-, [NCS]-, [NTf2]- and [BF4]-) were analyzed by electrochemical impedance spectroscopy (EIS) in…

Recent Advances on the Halo- and Cyano-Trifluoromethylation of Alkenes and Alkynes

2021

Incorporation of fluorine into organic molecules is a well-established strategy in the design of advanced materials, agrochemicals, and pharmaceuticals. Among numerous modern synthetic approaches, functionalization of unsaturated bonds with simultaneous addition of trifluoromethyl group along with other substituents is currently one of the most attractive methods undergoing wide-ranging development. In this review article, we discuss the most significant contributions made in this area during the last decade (2012−2021). The reactions reviewed in this work include chloro-, bromo-, iodo-, fluoro- and cyano-trifluoromethylation of alkenes and alkynes.

Asymmetric Michael Addition in Synthesis of β-Substituted GABA Derivatives

2022

γ-Aminobutyric acid (GABA) represents one of the most prolific structural units widely used in the design of modern pharmaceuticals. For example, β-substituted GABA derivatives are found in numerous neurological drugs, such as baclofen, phenibut, tolibut, pregabalin, phenylpiracetam, brivaracetam, and rolipram, to mention just a few. In this review, we critically discuss the literature data reported on the preparation of substituted GABA derivatives using the Michael addition reaction as a key synthetic transformation. Special attention is paid to asymmetric methods featuring synthetically useful stereochemical outcomes and operational simplicity. This research was funded by the National Na…

Approach Matters : The Kinetics of Interfacial Inverse-Electron Demand Diels-Alder Reactions

2017

Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels Alder (IEDDA) reactions represent a promising metal-free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained via a combination of XPS and surface-bound mass spectrometry (DART-MS).

Ionic Liquid Composite Polybenzimidazol Membranes for High Temperature PEMFC Applications

2019

A series of proton exchange membranes based on polybenzimidazole (PBI) were prepared using the low cost ionic liquids (ILs) derived from 1-butyl-3-methylimidazolium (BMIM) bearing different anions as conductive fillers in the polymeric matrix with the aim of enhancing the proton conductivity of PBI membranes. The composite membranes prepared by casting method (containing 5 wt. % of IL) exhibited good thermal, dimensional, mechanical, and oxidative stability for fuel cell applications. The effects of anion, temperature on the proton conductivity of phosphoric acid-doped membranes were systematically investigated by electrochemical impedance spectroscopy. The PBI composite membranes containin…

Experimental Study of the Oriented Immobilization of Antibodies on Photonic Sensing Structures by Using Protein A as an Intermediate Layer

2018

[EN] A proper antibody immobilization on a biosensor is a crucial step in order to obtain a high sensitivity to be able to detect low target analyte concentrations. In this paper, we present an experimental study of the immobilization process of antibodies as bioreceptors on a photonic ring resonator sensor. A protein A intermediate layer was created on the sensor surface in order to obtain an oriented immobilization of the antibodies, which enhances the interaction with the target antigens to be detected. The anti-bovine serum albumin (antiBSA)-bovine serum albumin (BSA) pair was used as a model for our study. An opto-fluidic setup was developed in order to flow the different reagents and,…

Enhanced Conductivity of Composite Membranes Based on Sulfonated Poly(Ether Ether Ketone) (SPEEK) with Zeolitic Imidazolate Frameworks (ZIFs)

2018

The zeolitic imidazolate frameworks (ZIFs) ZIF-8, ZIF-67, and a Zn/Co bimetallic mixture (ZMix) were synthesized and used as fillers in the preparation of composite sulfonated poly(ether ether ketone) (SPEEK) membranes. The presence of the ZIFs in the polymeric matrix enhanced proton transport relative to that observed for SPEEK or ZIFs alone. The real and imaginary parts of the complex conductivity were obtained by electrochemical impedance spectroscopy (EIS), and the temperature and frequency dependence of the real part of the conductivity were analyzed. The results at different temperatures show that the direct current (dc) conductivity was three orders of magnitude higher for composite …

Cycloaddition of Strained Cyclic Alkenes and Ortho-Quinones : A Distortion/Interaction Analysis

2020

The chemistry of strained unsaturated cyclic compounds has experienced remarkable growth in recent years via the development of metal–free click reactions. Among these reactions, the cycloaddition of cyclopropenes and their analogues to ortho-quinones has been established as a highly promising click reaction. The present work investigates the mechanism involved in the cycloaddition of strained dienes to ortho-quinones and structural factors that would influence this reaction. For this purpose, we use B97D density functional theory calculations throughout, and for relevant cases, we use spin component–scaled MP2 calculations and single–point domain-based local pair natural orbital coupled cl…

Diffusivity and free anion concentration of ionic liquid composite polybenzimidazole membranes.

2021

[EN] In this article, PBI composite membranes containing the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM-NTf2) at 1, 5, 10, 20 and 50 wt% (named PBI-IL-x) have been prepared by a casting method. The internal morphology of the membranes was analyzed by scanning electron microscopy (SEM), revealing that the incorporation of IL promotes the formation of porous channels. Thermal and mechanical stability was confirmed by thermogravimetric analysis (TGA) and tensile test measurements. The ionic transport through membranes was analysed by means of electrochemical impedance spectroscopy (EIS), showing a dependence on the IL loading, reaching a highest condu…

Asymmetric Synthesis of Fluorinated Monoterpenic Alkaloid Derivatives from Chiral Fluoroalkyl Aldimines via the Pauson‐Khand Reaction

2020

Hydrogen Production from Methanol-Water Solution and Pure Water Electrolysis Using Nanocomposite Perfluorinated Sulfocationic Membranes Modified by P…

2022

In this work, we report the preparation of Nafion membranes containing two different nanocomposite MF-4SC membranes, modified with polyaniline (PANI) by the casting method through two different polyaniline infiltration procedures. These membranes were evaluated as a polymer electrolyte membrane for water electrolysis. Operating conditions were optimized in terms of current density, stability, and methanol concentration. A study was made on the effects on the cell performance of various parameters, such as methanol concentration, water, and cell voltage. The energy required for pure water electrolysis was analyzed at different temperatures for the different membranes. Our experiments showed …

Phosphoric Acid Doped Polybenzimidazole (PBI)/Zeolitic Imidazolate Framework Composite Membranes with Significantly Enhanced Proton Conductivity unde…

2018

The preparation and characterization of composite polybenzimidazole (PBI) membranes containing zeolitic imidazolate framework 8 (ZIF-8) and zeolitic imidazolate framework 67 (ZIF-67) is reported. The phosphoric acid doped composite membranes display proton conductivity values that increase with increasing temperatures, maintaining their conductivity under anhydrous conditions. The addition of ZIF to the polymeric matrix enhances proton transport relative to the values observed for PBI and ZIFs alone. For example, the proton conductivity of PBI@ZIF-8 reaches 3.1 10&minus

Characterization of the laccase-mediated oligomerization of 4-hydroxybenzoic acid

2016

Modifying inert poly(ethersulfone) membranes using laccase has proven to be an environmentally benign and easily applicable process to alter the membrane's surface properties. By this method phenolic acid monomers such as 4-hydroxybenzoic acid are grafted from the membrane surface to make it anti-fouling. In order to enhance the anti-fouling capabilities even further it is important to study the molecular details of this reaction. However, the nature of the products of laccase modification, either on a surface or in solution, has been studied only poorly. In this paper we report the formation of C3–C3′, C3–O and C1–C3′ linked dimers as the first products of the solution-phase laccase-mediat…

Inside Cover: Strain-Promoted Cycloaddition of Cyclopropenes with o -Quinones: A Rapid Click Reaction (Angew. Chem. Int. Ed. 32/2018)

2018

Bis(imidazolium) salts derived from amino acids as receptors and transport agents for chloride anions

2015

The binding properties of bis(imidazolium) hosts 1a–c derived from amino acids towards different anions have been studied by 1H NMR titration experiments in 95 : 05 CD3CN : H2O at 303 K, ESI-MS and theoretical calculations. Among this family, the salt 1c showed a strong and high selectivity for chloride anions. Transmembrane chloride transport activity has also been studied for the three bis(imidazolium) based transporters in POPC liposome models, and compound 1a was identified as an active chloride/nitrate exchanger.

Coordination of Cu2+ Ions to C2 Symmetric Pseudopeptides Derived from Valine

2010

The acid-base and coordination properties of a family of pseudopeptidic ligands with C(2) symmetry derived from valine (4a-e) have been studied using a variety of techniques as a model for metal coordination in peptides and proteins. The Cu(2+) cation has been selected for coordination studies, although, for comparison, some results for Zn(2+) are also presented. Good agreement has been obtained between the results obtained by potentiometric titrations, spectroscopic analysis, and mass spectrometry (ESI) studies. These results highlight the potential for the use of ESI MS for characterizing the nature of the complex species formed. Clearly, the Cu(2+) complexes are much more stable than the…

Proton Conducting Electrospun Sulfonated Polyether Ether Ketone-Graphene Oxide Composite Membranes

2017

[EN] A series of novel composite membranes, based on sulfonated poly(ether ketone) (SPEEK) with a graphene oxide (GO) layer, were prepared. One contained a GO layer sandwiched between the SPEEK-polyvinyl alcohol (PVA) matrix (SPEEK/PVA@GO), and another deposited thin layers of GO on the nanofibers of SPEEK-polyvinyl butyral (PVB), with both sandwiched in the phase matrix of SPEEK-PVA (SPEEK/PVA@GO-NF). Various nanofiber thicknesses were studied by varying the electrospinning time. The prepared composite membranes with different nanofiber thicknesses were characterized by scanning electron microscopy, water uptake, ionic exchange capacity, thermogravimetric analysis, mechanical properties an…

Structural and Electrochemical Analysis of CIGS: Cr Crystalline Nanopowders and Thin Films Deposited onto ITO Substrates

2021

A new approach for the synthesis of nanopowders and thin films of CuInGaSe2 (CIGS) chalcopyrite material doped with different amounts of Cr is presented. The chalcopyrite material CuInxGa1 − xSe2 was doped using Cr to form a new doped chalcopyrite with the structure CuInxCryGa1 − x − ySe2, where x = 0.4 and y = 0.0, 0.1, 0.2, or 0.3. The electrical properties of CuInx CryGa1 − x − ySe2 are highly dependent on the Cr content and results show these materials as promising dopants for the fabrication thin film solar cells. The CIGS nano-precursor powder was initially synthesized via an autoclave method, and then converted into thin films over transparent substrates. Both crystalline precursor p…

Dual stereocontrolled alkylation of aldehydes with polystyrene-supported nickel complexes derived from α-amino amides

2015

Nickel(II) complexes derived from α-amino amide ligands anchored to gel-type and monolithic polymers act as efficient catalysts for the enantioselective addition of dialkylzinc reagents to aldehydes. Similar to the analogous homogeneous systems, dual stereocontrol in addition products can be achieved by controlling the stoichiometry of the immobilized nickel complex. Aromatic and aliphatic aldehydes were alkylated in good yields with enantioselectivities comparable to those obtained with the homogeneous analogues. These polymer-supported catalysts offer significant advantages as no metal leaching is observed and they can be easily recovered from the reaction mixture by simple filtration and…

Asymmetric Methods for Carbon‐Fluorine Bond Formation

2021

On the Stability and Formation of Pillar[n]arenes: a DFT Study

2021

The increased use of both pillar[5]arenes and pillar[6]arenes, stimulated by increasingly efficient syntheses of both, has brought forward the question as to what drives the intermediates in this Friedel-Crafts ring formation to form a pillar[5]arene, a pillar[6]arene, or any other sized macrocycle. This study sets out to answer this question by studying both the thermodynamics and kinetics involved in the absence and presence of templating solvents using high-end wB97XD/6-311G(2p,2d) DFT calculations.

CCDC 1972570: Experimental Crystal Structure Determination

2020

Related Article: Alberto Llobat, Jorge Escorihuela, Daniel M. Sedgwick, Miriam Rodenes, Raquel Román, Vadim A. Soloshonok, Jianlin Han, Mercedes Medio-Simón, Santos Fustero|2020|Eur.J.Org.Chem.|2020|4193|doi:10.1002/ejoc.202000598

CCDC 2067817: Experimental Crystal Structure Determination

2021

Related Article: Alberto Llobat, Jorge Escorihuela, Santos Fustero, Mercedes Medio-Simón|2021|Org.Lett.|23|3691|doi:10.1021/acs.orglett.1c01076

CCDC 1954729: Experimental Crystal Structure Determination

2020

Related Article: Alberto Llobat, Daniel M. Sedgwick, Albert Cabré, Raquel Román, Natalia Mateu, Jorge Escorihuela, Mercedes Medio‐Simón, Vadim Soloshonok, Jianlin Han, Antoni Riera, Santos Fustero|2020|Adv.Synth.Catal.|362 |1378 |doi:10.1002/adsc.201901504

CCDC 2067822: Experimental Crystal Structure Determination

2021

Related Article: Alberto Llobat, Jorge Escorihuela, Santos Fustero, Mercedes Medio-Simón|2021|Org.Lett.|23|3691|doi:10.1021/acs.orglett.1c01076