Browsing by Subject "Supramolecular chemistry"
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- PublicationOpen AccessEffective encapsulation of C60 by metal-organic frameworks with polyamide macrocyclic linkers(WILEY-VCH VERLAG GMBH, 2021) Saura-Sanmartin, Adrian; Martinez-Cuezva, Alberto; Marín-Luna, Marta; Bautista Cerezo, Delia; Berná Cánovas, José; Química OrgánicaA flexible benzylic amide macrocycle, functionalized with two carboxylic acid groups, was employed as the organic ligand for the preparation of robust copper(II)- and zinc(II)-based metal-organic frameworks. These polymers crystallized in the C2/m space group of the monoclinic crystal system, creating non-interpenetrated channels in one direction with an extraordinary solvent-accessible volume of 46%. Unlike metal-organic rotaxane frameworks having benzylic amide macrocycles as linkers, the absence of the thread in these novel reticular materials causes a decrease of dimensionality and an improvement of pore size and dynamic guest adaptability. We studied the incorporation of fullerene C60 inside the adjustable pocket generated between two macrocycles connected to the same dinuclear clusters, occupying a remarkable 98% of the cavities inside the network. The use of these materials as hosts for the selective recognition of different fullerenes was evaluated, mainly encapsulating the smaller size fullerene derivative in several mixtures of C60 and C70.
- PublicationOpen AccessEnantioselective Formation of 2-Azetidinones by Ring-Assisted Cyclization of Interlocked N-(alpha-Methyl)benzyl Fumaramides(WILEY-VCH VERLAG GMBH, 2018-04-16) Martinez-Cuezva, Alberto; Bautista, Delia; Alajarín, Mateo; Berná Cánovas, José; Química OrgánicaThe synthesis of optically active interlocked and non-interlocked 2-azetidinones by intramolecular cyclization of N-(alpha-methyl)benzyl fumaramide [2]rotaxanes is described. Two different strategies of asymmetric induction were tested in which the chiral group was located either proximal or distal to the reacting center of the thread. During these experiments, an interesting equilibration process inside the macrocyclic void occurred, thus leading to the cyclization through the (alpha-methyl)benzyl carbon atom and giving rise to beta-lactams, with a quaternary carbon atom, in an enantio- and diastereocontrolled manner. This cyclization also proceeds in kinetically stable chiral pseudo[2]rotaxanes, thus allowing further de threading to provide enantioenriched 3,4-disubstituted trans-2-azetidinones. The stereochemical outcomes of the cyclization inside and outside the macrocycle demonstrated noticeable
- PublicationOpen AccessExploring the Chemistry of the Mechanical Bond: Synthesis of a [2]Rotaxane through Multicomponent Reactions(American Chemical Society and Divisionof Chemical Education,Inc, 2023-08-01) Saura Sanmartín, Adrián; Lopez-Sanchez, Jorge; Lopez-Leonardo, Carmen; Pastor Vivero, Aurelia; Berná, José; Saura Sanmartín, Adrián; Berná, José; Química OrgánicaThe synthesis of a [2]rotaxane through three- or five-component coupling reactions has been adapted to an organic chemistry experiment for upper-division students. The experimental procedure addresses the search for the most favorable reaction conditions for the synthesis of the interlocked compound, which is obtained in a yield of up to 71%. Moreover, the interlocked nature of the rotaxane is proven by NMR spectroscopy. The content of the sessions has been designed on the basis of a proactive methodology whereby upper-division undergraduate students have a dynamic role. The laboratory experience not only introduces students to the chemistry of the mechanical bond but also reinforces their previous knowledge of basic organic laboratory procedures and their skills with structural elucidation techniques such as NMR and FT-IR spectroscopies. The experiment has been designed in such a customizable way that both experimental procedures and laboratory material can be adapted to a wide range of undergraduate course curricula.
PublicationOpen AccessFAIR data for compunds included in the article "Maximizing the [c2]daisy chain to lasso ratio through competitive self-templating clipping reactions"(Universidad de Murcia, 2021-11-30) Saura-Sanmartin, Adrian; Pastor Vivero, Aurelia; Martinez-Cuezva, Alberto; Berná Cánovas, José; Química Orgánica- PublicationOpen AccessMaximizing the [c2]daisy chain to lasso ratio through competitive self-templating clipping reactions(Royal Society of Chemistry, 2021-11-30) Saura-Sanmartin, Adrian; Pastor Vivero, Aurelia; Martinez-Cuezva, Alberto; Berná Cánovas, José; Química OrgánicaSelf-templating two-component coupling reactions allowed the isolation of two threaded products with different molecular sizes: a lasso-type [1]rotaxane and a [c2]daisy chain rotaxane. Their distribution in the final reaction mixture varies as a factor of the concentration of the reactants. Through this methodology we obtained a large 84-membered cyclic multistation [2]rotaxane.
- PublicationOpen AccessSynthesis of ‘Impossible’ Rotaxanes(Wiley-VCH GmbH, 2024-01-17) Saura Sanmartín, Adrián; Química Orgánica‘Impossible’ rotaxanes, which are constituted by interlocked components without obvious binding motifs, have attracted the interest of the mechanically interlocked molecules (MIMs) community. Within the synthetic efforts reported in the last decades towards the preparation of MIMs, some innovative protocols for accessing ‘impossible’ rotaxanes have been developed. This short review highlights different selected synthetic examples of ‘impossible’ rotaxanes, as well as suggests some future directions of this research area.
- PublicationOpen AccessThe Role of Dethreading Process in Pseudorotaxanes and Rotaxanes towards Advanced Applications: Recent Examples(Wiley-VCH, 2023-02-06) Saura-Sanmartín, Adrián; Química OrgánicaRotaxanes are a type of mechanically interlocked molecules (MIMs), constituted by at least a thread surrounded by a wheel, which are widely employed in the research field of artificial molecular machines. Although applications retaining the integrity of the mechanical bond are usually reported, the dethreading of the components can be crucial to develop some advanced applications. Thus, different dethreading strategies have been reported, and advanced applications which require such a process have turned out to be suitable approaches towards machine-like operation. This review article covers recent examples of applications of pseudorotaxanes and rotaxanes in which dethreading processes have a key role to accomplish the desired function.