Development of original synthetic strategies for the preparation of supramolecular Interlocked polymers

• Grant number: 13/22160-0
• Support Opportunities: Research Grants - Young Investigators Grants
• Start date: August 01, 2014
• End date: July 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry
• Principal Investigator: Jackson Dirceu Megiatto Junior
• Grantee: Jackson Dirceu Megiatto Junior
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Associated research grant(s): 21/06605-8 - Systems chemistry: controlling the complex behavior of mixtures of interacting molecules to develop molecular machines, interlocked polymers and new materials, AP.JP2
• Associated scholarship(s): 17/06752-5 - Development of New Template Strategies for the Synthesis of Polyrotaxanes, BP.DR

Abstract

The present research initiative describes synthetic strategies based on Coordination Chemistry that are expected to afford interlocked polymers with the necessary yield for preparation of bulky samples, which will allow the investigation of the many intriguing properties that will arise from the synergistic interactions between the interlocked component and the polymeric structure. Specifically, a new template synthesis based on metaloporphyrins axially-coordinated to nitrogenous Lewis bases is presented, which will allow the assembly, cyclization and polymerization processes to occur cooperatively in a convenient one-pot procedure to afford polyrotaxanes. Slight modifications of the template synthesis will allow the preparation of photoactive copolyrotaxanes composed of interlocked electron donor (D) and acceptor (A) subunits. The dynamic properties of the D-A copolyrotaxanes will be extensively investigated in order to understand the effects of molecular topology on the charge transport and on mechanoresponse properties of the materials. Further, the challenging synthesis of a polymer exclusively composed of catenane subunits will be targeted. A daring strategy that combines transion-metal template synthesis with dynamic covalent chemistry is proposed to achieve such elusive polycatenanes in an unprecedented all-in-protocol. A systematic investigation of the materials' properties using the facilities available in the Institute of Chemistry at Unicamp and abroad is described, which will pave the way for elaboration of new correlations between dynamic microstructural events in the interlocked macromolecules with their macro responses. In this connection, emergent properties such as damaging-sensing, super mechanical strength, nonlinear elastomeric and rheological behaviors, unique morphologies with intriguing charge and ion transport attributes and high-performance membranes are discussed on the basis of the molecular and supramolecular structures of the interlocked polymers. The success of the present research program will pave the way for the birth of a new field in polymer chemistry. (AU)

Scientific publications

(8)

(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)

ORNELAS-MEGIATTO, CATIA; BECHER, TIAGO B.; MEGIATTO, JR., JACKSON D.. Interlocked Systems in Nanomedicine. CURRENT TOPICS IN MEDICINAL CHEMISTRY, v. 15, n. 13, p. 1236-1256, 2015. (13/11519-7, 13/22160-0)

BERTUZZI, DIEGO L.; BECHER, TIAGO B.; CAPRETI, NAYLIL M. R.; AMORIM, JULIO; JURBERG, IGOR D.; MEGIATTO, JR., JACKSON D.; ORNELAS, CATIA. General Protocol to Obtain D-Glucosamine from Biomass Residues: Shrimp Shells, Cicada Sloughs and Cockroaches. GLOBAL CHALLENGES, v. 2, n. 11, NOV 2018. (18/02093-0, 15/04929-0, 17/24017-0, 14/15718-7, 13/22160-0)

MEGIATTO, JR., JACKSON D.; GULDI, DIRK M.; SCHUSTER, DAVID I.. Design, synthesis and photoinduced processes in molecular interlocked photosynthetic [60]fullerene systems. CHEMICAL SOCIETY REVIEWS, v. 49, n. 1, p. 8-20, JAN 7 2020. (13/22160-0)

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)

PERLI, GABRIEL; WANG, QI; BRAGA, CAROLYNE B.; BERTUZZI, DIEGO L.; FONTANA, LINIQUER A.; SOARES, MARCO C. P.; RUIZ, JAIME; MEGIATTO, JR., JACKSON D.; ASTRUC, DIDIER; ORNELAS, CATIA. Self-Assembly of a Triazolylferrocenyl Dendrimer in Water Yields Nontraditional Intrinsic Green Fluorescent Vesosomes for Nanotheranostic Applications. Journal of the American Chemical Society, v. 143, n. 33, p. 12948-12954, AUG 25 2021. (18/02093-0, 13/22160-0, 21/00555-9, 17/06146-8)

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.; 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)

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)