Title: Smart N-Heterocyclic Carbenes for Supramolecular Assemblies and Switchable Catalysts
Acronym of the project: (SMART-NHCs)
Funding entity: Ministerio de Ciencia e Innovación
Modality: PROYECTOS DE GENERACIÓN DE CONOCIMIENTO 2021
Entity code: PID2021-127862NB-I00
Principal researchers: 
  1. Eduardo Peris
  2. Macarena Poyatos
Dates: 2022-09-01 to 2025-08-31
Involved researchers: 
  1. Sergio Gonell Gómez
  2. Susana Ibáñez Maella
  3. Joel Martínez Visiedo
  4. Jairo Martinez
  5. Maite Silva Muñoz
  6. Marvin Linus Richter
  7. Cristian Leonardo Gutiérrez Peña
  8. César Luís Ruiz Zambrana
Summary/Abstract: 
Inspired by the host-guest chemistry events observed in nature, an impressive number of metal-based supramolecular architectures have been developed in the last three decades. For scientists seeking to design novel molecular materials exhibiting unusual sensing, magnetic, optical, and catalytic properties, and for researchers investigating the structure and function of biomolecules, supramolecular chemistry provides limitless possibilities. Therefore, supramolecular chemistry transcends the traditional divisional boundaries of science and represents a highly interdisciplinary field. The contemporary challenge of supramolecular chemists is now to control the functionalization of such molecular assemblies. This includes the capacity to design intricate ligands, which can act both as structural and functional building blocks, for the preparation of custom-made materials possessing one or more intentionally-programmed properties. In addition, the traditional role of spectator ligands that bind to the metal and provide electronic and steric-defined pockets for binding the substrate in homogeneous catalysis, switchable ligands incorporate stimuli-responsive units that can confer a biomimetic level of control over chemical transformations. Such level of control potentially enables these systems to facilitate chemical transformations that are difficult to accomplish in other ways, and therefore paves the way for tuning the catalysts to specific needs. Taking all this into account, this research proposal aims to merge the expertise of our research group in supramolecular organometallic chemistry and in homogeneous catalysis for developing two main research lines, aiming to a) develop new supramolecular assemblies for host-guest chemistry purposes and supramolecular catalysis, and b) design reversible switchable catalysts for specific catalytic transformations. These general objectives will be developed in four main work-packages: WP1) Developing modular frameworks for the rational design of SOCs with on-demand properties; WP2) Preparing new types of organometallic-based mechanically interlocked molecules (MIMs); WP3) Developing new types of double-pincer complexes; and WP4) Developing redox- and photo-switchable catalysts based on the decoration of N-heterocyclic carbene (NHC) ligands with rylene moieties (mostly naphthalene diimide, or perylene-diimide). For the development of the above mentioned WPs, we will base our systems in the use of N-heterocyclic carbenes (NHCs). Compared to traditional ligands NHCs are advantageous because: i) they provide kinetic/thermodynamic stable structures, due to the strength of the NHC-M bonds; ii) they can facilitate the incorporation of extended -conjugated systems, thus allowing the construction of supramolecular structures with magnified -stacking interactions; and iii) they are extremely versatile from the coordination point of view, meaning that they constitute an ideal building block for a modular approach of a large variety of metallocages with diverse geometries and functionalities.