Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction

Valentini, Matteo; Melchiorre, Gabriele; Spatola, Emanuele; Stefano, Stefano Di

doi:10.1002/chem.202200685

Cited by 23 publications

(22 citation statements)

References 126 publications

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“…Another example of TDDL that can be described with the scheme depicted in Figure 3 was reported by Di Stefano and coworkers [29] …”

Section: Thermodynamic Dissipative Dynamic Library (Tddl)mentioning

confidence: 96%

“…Another example of TDDL that can be described with the scheme depicted in Figure 3 was reported by Di Stefano and coworkers. [29] In this case, reversibility of the imine chemistry is initially exploited to generate a minimal DL consisting of alkylimine 16 and arylimine 17 and the corresponding amines (Figure 11a). In the absence of any added fuel the composition of the DL (DL 0 ) is strongly shifted to the side of alkylimine 16.…”

Section: Thermodynamic Dissipative Dynamic Library (Tddl)mentioning

confidence: 99%

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Dissipative Dynamic Libraries (DDLs) and Dissipative Dynamic Combinatorial Chemistry (DDCC)

et al. 2022

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This Concept is focused on the key features of dissipative dynamic combinatorial chemistry (DDCC). DDCC deals with transient libraries of compounds, maintained out‐of‐equilibrium by the consumption of a fuel, whose composition changes upon the selection pressure of kinetic and/or thermodynamic processes. Concepts and definitions of kinetic and thermodynamic dissipative dynamic libraries (“KDDL” and “TDDL”), are introduced and illustrated by a number of actual cases, thus showing the consistency of the present approach. Such concepts and definitions can help establish a common language for this emerging field, which, in our view, has the potential to become highly relevant to supramolecular chemistry.

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“…Another example of TDDL that can be described with the scheme depicted in Figure 3 was reported by Di Stefano and coworkers [29] …”

Section: Thermodynamic Dissipative Dynamic Library (Tddl)mentioning

confidence: 96%

Section: Thermodynamic Dissipative Dynamic Library (Tddl)mentioning

confidence: 99%

Dissipative Dynamic Libraries (DDLs) and Dissipative Dynamic Combinatorial Chemistry (DDCC)

et al. 2022

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“…The same hydrazone−disulfide energy ratchet was then applied to achieve a system in which a biphenyl based crown ether is able to read the chiral information contained in a molecular wire defined as a "molecular tape". 22 Both kind of ACAs, fuels 1a−d and 2, were also applied to finely control the conformation of calix [4]arene cone scaffolds endowed with two amino functions at two opposite positions of the upper rim (see 10 and 11 in Figure 4b). In particular, a time programmable locking/unlocking of the 10 scaffold was achieved using fuels 1a−d.…”

Section: ■ Dissipative Systems Driven By Acas Molecular Switches and ...mentioning

confidence: 99%

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Stefano

2023

Acc. Chem. Res.

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Conspectus The 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.

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“…In this context, since 2016, the group of Di Stefano and later the one of Schmittel have applied different 2-cyano-2-arylpropanoic acids to fuel different dissipative systems such as catenane switches (Scheme c). − Such acids are interesting given the modularity of the aromatic group influencing the kinetics of decarboxylation, but generating 2-aryl-acetonitriles as accumulating side-product, a nonvolatile waste nonremovable from the system. The use of nitroacetic acid in water nicely complements these acids and provides nitromethane as waste.…”

Section: Trichloroacetic Acid As Chemical Fuel For Conformational Swi...mentioning

confidence: 99%

Out of Equilibrium Chemical Systems Fueled by Trichloroacetic Acid

Olivieri

Quintard

2022

ACS Org. Inorg. Au

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Dissipative systems are based on the supply of energy to a system by fuel pulses and dissipation of this energy through the fuel decomposition, resulting in repetition of a given physical or biological function. Such out of equilibrium processes are at the heart of all living organisms, and in the past decade, researchers have attempted to transpose these principles to purely synthetic systems. However, upon fuel decomposition, the resulting waste generated tends to accumulate in the system, rapidly inhibiting the machinery after a few cycles of fuel pulses. In order to solve this issue, trichloroacetic acid has appeared as a fuel of choice to reversibly change the acidity of a system, liberating volatile chloroform and CO2 upon fuel decomposition. In this Perspective, we present the advantages of this fuel and successful applications ranging from conformational switches to rotary motors to temporal control over crystallization or smart materials.

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Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction

Cited by 23 publications

References 126 publications

Dissipative Dynamic Libraries (DDLs) and Dissipative Dynamic Combinatorial Chemistry (DDCC)

Dissipative Dynamic Libraries (DDLs) and Dissipative Dynamic Combinatorial Chemistry (DDCC)

Dissipative Systems Driven by the Decarboxylation of Activated Carboxylic Acids

Out of Equilibrium Chemical Systems Fueled by Trichloroacetic Acid

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