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Development of New Template Strategies for the Synthesis of Polyrotaxanes

Grant number: 17/06752-5
Support type:Scholarships in Brazil - Doctorate
Effective date (Start): June 01, 2017
Effective date (End): May 31, 2020
Field of knowledge:Physical Sciences and Mathematics - Chemistry
Cooperation agreement: Coordination of Improvement of Higher Education Personnel (CAPES)
Principal Investigator:Jackson Dirceu Megiatto Junior
Grantee:Liniquer Andre Fontana
Home Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
Associated research grant:13/22160-0 - Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers, AP.JP


This PhD project is part of a multidisciplinary research program funded by Fapesp at Jovem Pesquisador category (project number 2013/22160-0), whose main goal is to afford unique interlocked polymers, namely polyrotaxanes and polycatenantes. Rotaxanes are super structures composed of a macromolecular ring threaded by a molecular axle component bearing bulky substituents at both termini that avoid dissociation of the interlocked or mechanically linked components. The most remarkable feature of rotaxanes is the possibility to control the molecular motions of one component relative to the other. For example, the rotaxane structure brings about at least two new and peculiar degrees of freedom, namely the rotation and/or translation of the macrocycle ring relative to the thread that do not exist in the noninterlocked architectures. If rotaxanes could be linked together in a polymer-like structure, such molecular movements will possibly reflect positively in the macroscopic properties of the polymer materials. However, preparation of organized polyrotaxanes is still a synthetic challenge as the entropy cost to assemble such highly ordered interlocked polymer is prohibitive. Herein, it is described a new metal template synthetic strategy based on innovative Ru(II)porphyrinates specifically linked to aromatic moieties to yield a well-defined cavity of the macrocycle component of rotaxanes. Coordination of Ru(II) ions to the porphyrin core along with coordination of apical ligands are expected to occur and will afford a special catalyst able to promote cyclopropanation reactions inside the macrocycle cavity's only; a crucial requisite to our approach towards polyrotaxanes. (AU)

Scientific publications
(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)
ALCANTARA, ARTHUR F. P.; FONTANA, LINIQUER A.; RIGOLIN, VITOR H.; ANDRADE, YURI F. S.; RIBEIRO, MARCOS A.; BARROS, WDESON P.; ORNELAS, CATIA; MEGIATTO, JR., JACKSON D. Olefin Cyclopropanation by Radical Carbene Transfer Reactions Promoted by Cobalt(II)/Porphyrinates: Active-Metal-Template Synthesis of [2]Rotaxanes. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, v. 57, n. 29, p. 8979-8983, JUL 16 2018. Web of Science Citations: 2.

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