Development of New Template Strategies for the Synthesis of Polyrotaxanes

• Grant number: 17/06752-5
• Support Opportunities: Scholarships in Brazil - Doctorate
• Start date: June 01, 2017
• End date: July 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry
• Agreement: Coordination of Improvement of Higher Education Personnel (CAPES)
• Principal Investigator: Jackson Dirceu Megiatto Junior
• Grantee: Liniquer André Fontana
• Host 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

Abstract

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

(4)

(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.; ALMEIDA, MARLON P.; RIGOLIN, VITOR H.; RIBEIRO, MARCOS A.; BARROS, WDESON P.; MEGIATTO, JR., JACKSON D.. Control over the Redox Cooperative Mechanism of Radical Carbene Transfer Reactions for the Efficient Active-Metal-Template Synthesis of [2]Rotaxanes. CHEMISTRY-A EUROPEAN JOURNAL, v. 26, n. 35, p. 7808-7822, JUN 23 2020. (17/06752-5, 15/23761-2, 13/22160-0)

FONTANA, LINIQUER A.; ALMEIDA, MARLON P.; ALCANTARA, ARTHUR F. P.; RIGOLIN, VITOR H.; RIBEIRO, MARCOS A.; BARROS, WDESON P.; MEGIATTO, JACKSON D.. Ru(II)Porphyrinate-based molecular nanoreactor for carbene insertion reactions and quantitative formation of rotaxanes by active-metal-template syntheses. NATURE COMMUNICATIONS, v. 11, n. 1, DEC 11 2020. (17/06752-5, 13/22160-0, 15/23761-2)

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. (15/23761-2, 13/22160-0, 15/22379-7, 17/06752-5)

FONTANA, LINIQUER A.; RIGOLIN, VITOR H.; RIBEIRO, MARCOS A.; BARROS, WDESON P.; MEGIATTO, JACKSON D., JR.. A synthetic tactic to substitute axial ligands in sterically demanding Ru(ii)porphyrinates. DALTON TRANSACTIONS, v. 51, n. 26, p. 7-pg., 2022-06-16. (17/06752-5, 13/22160-0, 20/09280-0, 21/06605-8)

Academic Publications

(References retrieved automatically from State of São Paulo Research Institutions)

FONTANA, Liniquer André. Development of new synthetic strategies for the preparation of polyrotaxanes. 2022. Doctoral Thesis - Universidade Estadual de Campinas (UNICAMP). Instituto de Química Campinas, SP.