RESUMEN
Oscillating reactions are among the most intriguing phenomena in chemistry, but many questions on their mechanisms still remain unanswered, due to their intrinsic complexity and to the low sensitivity of the most common spectroscopic techniques toward the reaction brominated species. In this work, we investigate the cerium ion-catalyzed Belousov-Zhabotinsky (BZ) oscillating reaction by means of time-resolved X-ray absorption spectroscopy (XAS), in combination with UV-vis spectroscopy and unsupervised machine learning, multivariate curve resolution, and kinetic analyses. Altogether, we provide new insights into the collective oscillatory behavior of the key brominated species involved in the classical BZ reaction and measure previously unreported oscillations in their concentrations through Br K-edge XAS, while simultaneously tracking the oscillatory Ce4+-to-Ce3+ transformation by coupling XAS with UV-vis spectroscopy. Our work evidences the potential of the XAS technique to investigate the mechanisms of oscillatory chemical systems whose species are often not detectable with conventional experimental methods.
RESUMEN
Brønsted basicity is a fundamental chemical property featured by several kinds of inorganic and organic compounds. In this Review, we treat a particularly high basicity resulting from the mechanical entanglement involving two or more molecular subunits in catenanes and rotaxanes. Such entanglement allows a number of basic sites to be in close proximity with each other, highly increasing the proton affinity in comparison with the corresponding, non-entangled counterparts up to obtain superbases, properly defined as mechanically interlocked superbases. In the following pages, the development of this kind of superbases will be described with a historical perusal, starting from the initial, serendipitous findings up to the most recent reports where the strong basic property of entangled molecular units is the object of a rational design.
RESUMEN
A well-behaved dynamic library composed of two imines and corresponding amines was subjected to the action of an activated carboxylic acid (ACA), whose decarboxylation is known to be base promoted, in different solvents, namely CD2Cl2, CD3CN, and mixtures of them. Two non-equilibrium systems are consequently obtained: i)â a dissipative (CD2Cl2) and ii)â an out-of-equilibrium (CD3CN) dynamic library whose composition goes back to equilibrium after a given time. In the former case, the library is fully coupled with the decarboxylation of the ACA, while in the latter, an energy ratchet operates. In the mixed solvents, the library exhibits a mediated behavior. Interestingly, in the presence of an excess of added ACA, the different behavior of the imine library in the two solvents is expected to manifest only when the excess acid is consumed.
RESUMEN
Precise control of substrate positioning and orientation (its proximity to the reactive unit) is often invoked to rationalize the superior enzymatic reaction rates and selectivities when compared to synthetic models. Artificial nonheme iron (IV) oxo (Fe(IV)=O) complexes react with C(sp3)-H bonds via a biomimetic Hydrogen Atom Transfer/Hydroxyl Rebound mechanism, but rates, site-selectivity and even hydroxyl rebound efficiency (ligand rebound versus substrate radical diffusion) are smaller than in oxygenases. Herein, we quantitatively analyze how substrate binding modulates nonheme Fe(IV)=O reactivity by comparing rates and outcomes of C-H oxidation by a pair of Fe(IV)=O complexes that share the same first coordination sphere but only one contains a crown ether receptor that recognizes the substrate. Substrate binding makes the reaction intramolecular, exhibiting Michaelis-Menten kinetics and increased reaction rates. In addition, C-H oxidation occurs with high site selectivity for remote sites. Analysis of Effective Molarity reveals that the system operates at its maximal theoretical capability for the oxidation of these remote sites. Remarkably, substrate positioning also affects Hydroxyl Rebound, whose efficiency only increases on the sites placed in proximity by recognition. Overall, these observations provide evidence that supramolecular control of substrate positioning can effectively modulate the reactivity of oxygenases and its models.
RESUMEN
The use of Activated Carboxylic Acids (ACAs) allows the time-controlled operation of dissipative chemical systems based on the acid-base reaction by providing both the stimulus that temporarily drives a physicochemical change and, subsequently, the counter-stimulus with a single reagent addition. However, their application is inherently limited to acid-sensitive systems. To overcome this limitation, we herein develop a straightforward device for the transduction of the acid-base stimuli delivered by an ACA into a voltage signal that, in turn, is used to control voltage-sensitive circuits that are not pH-responsive by themselves. The signal transductor can be easily assembled from common laboratory equipment and employs aqueous solutions of readily available chemicals. Furthermore, the operator can simply and intuitively tune the amplitude of the voltage signal, as well as its duration and offset by varying the concentration of the chemical species involved in the transduction process.
RESUMEN
The operation of a dissipative network composed of two or three different crown-ether receptors and an alkali metal cation can be temporally driven by the use (combined or not) of two orthogonal stimuli of a different nature. More specifically, irradiation with light at a proper wavelength and/or addition of an activated carboxylic acid, are used to modulate the binding capability of the above crown-ethers towards the metal ion, allowing to control over time the occupancy of the metal cation in the crown-ether moiety of a given ligand. Thus, application of either or both of the stimuli to an initially equilibrated system, where the metal cation is distributed among the crown-ether receptors depending on the different affinities, causes a programmable change in the receptor occupancies. Consequently, the system is induced to evolve to one or more out-of-equilibrium states with different distributions of the metal cation among the different receptors. When the fuel is exhausted or/and the irradiation interrupted, the system reversibly and autonomously goes back to the initial equilibrium state. Such results may contribute to the achievement of new dissipative systems that, taking advantage of multiple and orthogonal stimuli, are featured with more sophisticated operating mechanisms and time programmability.
RESUMEN
Site-selective oxidation of aliphatic C-H bonds is a powerful synthetic tool because it enables rapid build-up of product complexity and diversity from simple precursors. Besides the poor reactivity of alkyl C-H bonds, the main challenge in this reaction consists in differentiating between the multiple similar sites present in most organic molecules. Herein, a manganese oxidation catalyst equipped with two 18-benzo-6-crown ether receptors has been employed in the oxidation of the long chain tetradecane-1,14-diamine. 1H-NMR studies evidence simultaneous binding of the two protonated amine moieties to the crown ether receptors. This recognition has been used to pursue site-selective oxidation of a methylenic site, using hydrogen peroxide as oxidant in the presence of carboxylic acids as co-ligands. Excellent site-selectivity towards the central methylenic sites (C6 and C7) is observed, overcoming selectivity parameters derived from polar deactivation by simple amine protonation and selectivity observed in the oxidation of related monoprotonated amines.
RESUMEN
ConspectusThe achievement of artificial systems capable of being maintained in out-of-equilibrium states featuring functional properties is a main goal of current chemical research. Absorption of electromagnetic radiation or consumption of a chemical species (a "chemical fuel") are the two strategies typically employed to reach such out-of-equilibrium states, which have to persist as long as one of the above stimuli is present. For this reason such systems are often referred to as "dissipative systems". In the simplest scheme, the dissipative system is initially found in a resting, equilibrium state. The addition of a chemical fuel causes the system to shift to an out-of-equilibrium state. When the fuel is exhausted, the system reverts to the initial, equilibrium state. Thus, from a mechanistic standpoint, the dissipative system turns out to be a catalyst for the fuel consumption. It has to be noted that, although very simple, this scheme implies the chance to temporally control the dissipative system. In principle, modulating the nature and/or the amount of the chemical fuel added, one can have full control of the time spent by the system in the out-of-equilibrium state.In 2016, we found that 2-cyano-2-phenylpropanoic acid (1a), whose decarboxylation proceeds smoothly under mild basic conditions, could be used as a chemical fuel to drive the back and forth motion of a catenane-based molecular switch. The acid donates a proton to the catenane that passes from the neutral state A to the transient protonated state B. Decarboxylation of the resulting carboxylate (1acb), generates a carbanion, which, being a strong base, retakes the proton from the protonated catenane that, consequently, returns to the initial state A. The larger the amount of the added fuel, the longer the time spent by the catenane in the transient, out-of-equilibrium state. Since then, acid 1a and other activated carboxylic acids (ACAs) have been used to drive the operation of a large number of dissipative systems based on the acid-base reaction, from molecular machines to host-guest systems, from catalysts to smart materials, and so on. This Account illustrates such systems with the purpose to show the wide applicability of ACAs as chemical fuels. This generality is due to the simplicity of the idea underlying the operation principle of ACAs, which always translates into simple experimental requirements.
RESUMEN
Temporal control of molecular motions is receiving increasing attention because it is central to the development of molecular switches and motors and nanoscopic materials with life-like properties. Inspired by previous studies, here, we report that acid 12 can be used to temporally control the conformational freedom around the C-C bond connecting the two aromatic rings of the ditopic bases 4 and 5. Consistent with NMR measurements and DFT calculations, before fuel addition, the conformational motion of the two aromatic rings of both 4 and 5 mainly consists of a large amplitude torsional oscillation spanning about 260° and passing for the anti conformation (the two nitrogen atoms at opposite sides). Immediately after the addition of 12, due to the protonation of one nitrogen and consequent formation of an N-H···N intramolecular hydrogen bond, the torsional oscillation in both 4H+ and 5H+ is not only restricted to a smaller range (about 100°) but explores the previously forbidden conformational space around the syn conformation (the two nitrogen atoms at the same side). However, the new state is an out-of-equilibrium state since decarboxylation of the conjugate base of 12 takes place and, at the end of the process, the system reverts to the more conformationally mobile state.
RESUMEN
Hydrogel actuators are important for designing stimuli-sensitive soft robots. They generate mechanical motion by exploiting compartmentalized (de)swelling in response to a stimulus. However, classical switching methods, such as manually lowering or increasing the pH, cannot provide more complex autonomous motions. By coupling an autonomously operating pH-flip with programmable lifetimes to a hydrogel system containing pH-responsive and non-responsive compartments, autoonenomous forward and backward motion as well as more complex tasks, such as interlocking of "puzzle pieces" and collection of objects are realized. All operations are initiated by one simple trigger, and the devices operate in a "fire and forget" mode. More complex self-regulatory behavior is obtained by adding chemo-mechano-chemo feedback mechanisms. Due to its simplicity, this method shows great potential for the autonomous operation of soft grippers and metamaterials.
RESUMEN
The dissipative translocation of the Zn2+ ion between two prototypical coordination complexes has been investigated by combining X-ray absorption and 1H NMR spectroscopy. An integrated experimental and theoretical approach, based on state-of-the-art Multivariate Curve Resolution and DFT based theoretical analyses, is presented as a means to understand the concentration time evolution of all relevant Zn and organic species in the investigated processes, and accurately characterize the solution structures of the key metal coordination complexes. Specifically, we investigate the dissipative translocation of the Zn2+ cation from hexaaza-18-crown-6 to two terpyridine moieties and back again to hexaaza-18-crown-6 using 2-cyano-2-phenylpropanoic acid and its para-chloro derivative as fuels. Our interdisciplinary approach has been proven to be a valuable tool to shed light on reactive systems containing metal ions that are silent to other spectroscopic methods. These combined experimental approaches will enable future applications to chemical and biological systems in a predictive manner.
Asunto(s)
Complejos de Coordinación , Cationes , Complejos de Coordinación/química , Cristalografía por Rayos X , Ligandos , Espectroscopía de Resonancia Magnética , Metales , Rayos X , Zinc/químicaRESUMEN
This work reports that the composition of a dynamic library (DL) of interconverting imines can be controlled over time in a dissipative fashion by the addition of an activated carboxylic acid used as a chemical fuel. When the fuel is added to the DL, which is initially under thermodynamic equilibrium, the composition of the mixture dramatically changes and a new, dissipative (out of equilibrium) state is reached that persists until fuel exhaustion. Thus, a transient dissipative dynamic library (DDL) is generated that, eventually, reverts back to the initial DL when the fuel is consumed, closing a DLâDDLâDL cycle. The larger the amount of added fuel, the longer the time spent by the system in the DDL state. The transimination reaction is shown to be an optimal candidate for the realization of a dissipative dynamic covalent chemistry (DDCvC).
RESUMEN
The host-guest interaction of a 1,3,5-trisaminocalix[6]arene receptor with N-methylisoquinolinium trifluoromethanesulfonate (Kass of 500 ± 30 M-1 in CD2Cl2) can be dissipatively driven by means of 2-cyano-2-(4'-chloro)phenylpropanoic acid used as a convenient chemical fuel. When the fuel is added to a dichloromethane solution containing the above complex, the host is induced to immediately release the guest in the bulk solution. Consumption of the fuel allows the guest to be re-uptaken by the host. The operation can be satisfactorily reiterated with four subsequent additions of fuel, producing four successive release-reuptake cycles. The percentage of the guest temporarily released in the bulk solution by the host and the time required for the reuptake process can be finely regulated by varying the quantities of added fuel.
RESUMEN
The satisfactory rationalization of complex reactive pathways in solution chemistry may greatly benefit from the combined use of advanced experimental and theoretical complementary methods of analysis. In this work, we combine X-Ray Absorption and 1 Hâ NMR spectroscopies with state-of-the-art Multivariate Curve Resolution and theoretical analyses to gain a comprehensive view on a prototypical reaction involving the variation of the oxidation state and local structure environment of a selected metal ion coordinated by organic ligands. Specifically, we investigate the 2-cyano-2-phenylpropanoic acid reduction of the octahedral complex established by the Cu2+ ion with terpyridine to the tetrahedral complex formed by Cu+ and neocuproine. Through our interdisciplinary approach we gain insights into the nature, concentration time evolution and structures of the key metal (XAS measurements) and organic (1 H NMR measurements) species under reaction. We believe our method may prove to be useful in the toolbox necessary to understand the mechanisms of reactive processes of interest in solution.
RESUMEN
The temporal control (ON/OFF/ON) of the fluorescence of a dichloromethane/acetonitrile 1 : 1 solution of calixarene 3 decorated with two pyrenyl moieties at the upper rim is attained by the addition of CCl3CO2H used as a convenient chemical fuel.
RESUMEN
We demonstrate here the use of 2-(4-chlorophenyl)-2-cyanopropanoic acid (CPA) and nitroacetic acid (NAA) as convenient chemical fuels to drive the dissipative operation of DNA-based nanodevices. Addition of either of the fuel acids to a water solution initially causes a rapid transient pH decrease, which is then followed by a slower pH increase. We have employed such low-to-high pH cycles to control in a dissipative way the operation of two model DNA-based nanodevices: a DNA nanoswitch undergoing time-programmable open-close-open cycles of motion, and a DNA-based receptor able to release-uptake a DNA cargo strand. The kinetics of the transient operation of both systems can be easily modulated by varying the concentration of the acid fuel added to the solution and both acid fuels show an efficient reversibility which further supports their versatility.
RESUMEN
A kinetic analysis of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the iron(IV)-oxo complex [(N4Py)FeIV(O)]2+ and to the phthalimide N-oxyl radical (PINO) has been carried out. The results indicate that a higher activating effect of α-heteroatoms toward the HAT from C-H bonds is observed with the more electrophilic PINO radical. When the N-hydroxy precursor of PINO, N-hydroxyphthalimide (NHPI), is used as a HAT mediator in the oxidation promoted by [(N4Py)FeIV(O)]2+, significant differences in terms of selectivity have been found. Product studies of the competitive oxidations of primary and secondary aliphatic alcohols (1-decanol, cyclopentanol, and cyclohexanol) with alkylaromatics (ethylbenzene and diphenylmethane) demonstrated that it is possible to modify the selectivity of the oxidations promoted by [(N4Py)FeIV(O)]2+ in the presence of NHPI. In fact, alkylaromatic substrates are more reactive in the absence of the mediator while alcohols are preferably oxidized in the presence of NHPI.
RESUMEN
In this report it is shown that nitroacetic acid 1 (O2NCH2CO2H) can be conveniently used to control the pH of a water solution over time. Time-programmable sequences of the kind pH1(high)-pH2(low)-pH3(high) can be achieved, where both the extent of the initial pH jump (pH1(high)-pH2(low)) and the time required for the subsequent pH rising (pH2(low)-pH3(high)) can be predictably controlled by a judicious choice of the absolute and relative concentrations of the reagents (acid 1 and NaOH). Successive pH1(high)-pH2(low)-pH3(high) sequences can be obtained by subsequent additions of acid 1. As a proof of concept, the method is applied to control over time the pH-dependent host-guest interaction between alpha-cyclodextrin and p-aminobenzoic acid.
RESUMEN
The adoption of a supramolecular approach in catalysis promises to address a number of unmet challenges, ranging from activity (unlocking of novel reaction pathways) to selectivity (alteration of the innate selectivity of a reaction, e.g. selective functionalization of C-H bonds) and regulation (switch ON/OFF, sequential catalysis, etc.). Supramolecular tools such as reversible association and recognition, pre-organization of reactants and stabilization of transition states upon binding offer a unique chance to achieve the above goals disclosing new horizons whose potential is being increasingly recognized and used, sometimes reaching the degree of ripeness for practical use. This review summarizes the main developments that have opened such new frontiers, with the aim of providing a guide to researchers approaching the field. We focus on artificial supramolecular catalysts of defined stoichiometry which, under homogeneous conditions, unlock outcomes that are highly difficult if not impossible to attain otherwise, namely unnatural reactivity or selectivity and catalysis regulation. The different strategies recently explored in supramolecular catalysis are concisely presented, and, for each one, a single or very few examples is/are described (mainly last 10 years, with only milestone older works discussed). The subject is divided into four sections in light of the key design principle: (i) nanoconfinement of reactants, (ii) recognition-driven catalysis, (iii) catalysis regulation by molecular machines and (iv) processive catalysis.
RESUMEN
In this work, we obtain detailed mechanistic and structural information on bimolecular chemical reactions occurring in solution on the second to millisecond time scales through the combination of a statistical, multivariate and theoretical analysis of time-resolved coupled X-ray Absorption Spectroscopy (XAS) and UV-Vis data. We apply this innovative method to investigate the sulfoxidation of p-cyanothioanisole and p-methoxythioanisole by the nonheme FeIV oxo complex [N4Py·FeIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile at room temperature. By employing statistical and multivariate techniques we determine the number of key chemical species involved along the reaction paths and derive spectral and concentration profiles for the reaction intermediates. From the quantitative analysis of the XAS spectra we obtain accurate structural information for all reaction intermediates and provide the first structural characterization in solution of complex [N4Py·FeIII(OH)]2+. The employed strategy is promising for the spectroscopic characterization of transient species formed in redox reactions.