The back and forth motions of a crown-ether based wheel along the axis of a bistable rotaxane are triggered by the decarboxylation of 2-cyano-2-phenylpropanoic acid and detected by the oscillation of the EPR nitrogen splitting of a dialkyl nitroxide function mounted within the macrocyclic ring. When the -Cl derivative of the acid is used, back and forth motions are accelerated. Conversely, with CH and -OCH derivatives, the back motion is strongly inhibited by the insurgence of collateral radical reactions.
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http://dx.doi.org/10.1021/acs.joc.9b01164 | DOI Listing |
Acc Chem Res
April 2023
Dipartimento di Chimica and ISB-CNR Sede Secondaria di Roma - Meccanismi di Reazione, Università degli Studi di Roma "La Sapienza", P.le A. Moro 5, 00185 Rome, Italy.
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".
View Article and Find Full Text PDFJ Phys Chem Lett
June 2022
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza", P.le A. Moro 5, I-00185 Rome, Italy.
The dissipative translocation of the Zn ion between two prototypical coordination complexes has been investigated by combining X-ray absorption and H 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 Zn 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 -chloro derivative as fuels.
View Article and Find Full Text PDFChemistry
January 2022
Dipartimento di Chimica, Università degli Studi di Roma "La Sapienza", P.le A. Moro 5, I-00185, Rome, Italy.
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 H 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 Cu ion with terpyridine to the tetrahedral complex formed by Cu and neocuproine.
View Article and Find Full Text PDFJ Am Chem Soc
September 2021
Organische Chemie I, Center of Micro- and Nanochemistry and Engineering, University of Siegen, Adolf-Reichwein-Str. 2, D-57068 Siegen, Germany.
J Am Chem Soc
April 2021
Center of Micro- and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany.
A 3-fold completive self-sorted library of dynamic motifs was integrated into the design of the pseudorotaxane-based rotor [Zn(·H)()()] operating at = 15.4 kHz. The rotational motion in the five-component device is based on association/dissociation of the pyridyl head of the pseudorotaxane rotator arm between two zinc(II) porphyrin stations.
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