e-POMOCOL

MFA-2022-057

This project has two clearly differentiated lines of work, which are:

1. Development of materials for the generation of renewable energy

Splitting water into hydrogen and oxygen using solar energy is the simplest approach to produce renewable fuels. The generation of eco-friendly H₂ from water comprises two half reactions: (i) the oxidation of two water molecules into O₂ and (ii) water reduction, which converts protons and electrons into molecular H₂. An important drawback of these half-reactions is their slow kinetics, especially for the oxygen evolution reaction (OER), leading to a low overall energy conversion efficiency. As a consequence, there is currently an extraordinary research activity devoted to the development of efficient, robust and low-cost water oxidation catalysts (WOCs).

Our first general objective is to solve this problem by using polyoxometalates (POMs) and POM-based Metal Organic Frameworks (POMOFs) as catalysts for the OER. POMs are a large class of anionic metal oxide clusters (mainly of Mo and W) that exhibit reversible charge transfer without structural change, making them very attractive for photoelectrocatalytic applications.

A second objective within this line of work is the design and synthesis of LDH-based catalysts for energy-conversion reactions by tuning the composition of the material and creating structural defects and their calcination to obtain oxides stable in high temperature conditions. Preparation of LDH-metal oxides heterostructures that create synergies and promote charge separation and transport.

2. Development of materials for energy storage.

A considerable effort is currently being made in order to develop functional hydrogen storage materials. Among these, porous adsorbents such as metal-organic frameworks (MOFs) could offer the fastest filling times at the lowest delivery pressures. In order to improve the gravimetric storage capacity of H₂, transition metal nodes can be replaced by lighter atoms, such as carbon and nitrogen. These covalent organic frameworks (COFs) exhibit higher stabilities as compared to MOFs. One of the drawbacks of this approach is that, in order to achieve crystallinity, reversible reactions between organic building blocks must be employed, limiting the scope of the method.

The third general objective of the project is to increase hydrogen storage capacities and strengthen adsorption interactions by using a hybrid MOF/COF approach with a three-fold aim: (i) to obtain multifunctional networks with open metal sites and strong thermodynamic stability; (ii) to introduce a novel topochemical route for the preparation of COF materials with higher crystallinity; (iii) to tune the pore characteristics of the sorbent material (diameter, shape, opening) in an unprecedented way via electrochemical potential (using redox-active metal nodes) or light irradiation (using spin crossover metal centres).

To achieve this objective and to ensure crystallinity and proper characterization of the materials, we aim to introduce a novel synthetic procedure based on the pre-assembly of the building units via dihydrogen bonds, followed by a topochemical dehydrogenation reaction.

Photocatalysts,electrocatalysts,energy conversión reactions,polyoxometalates, ayered double hydroxides,H-bonded networks,Covalent Organic Frameworks,Hydrogen storage

Manuel Molina Muriel - Polytechnic University of Valencia

(mamomu@doctor.upv.es)

Department of Inorganic Chemistry

Faculty of Chemistry (Building F, 3rd floor)

C/ Dr. Moliner, 50

46100 Burjassot (Valencia)

Carlos.gomez@uv.es

Teléfono: 963 544 423

GVA

Plan de Recuperación, Transformación y Resilencia del Gobierno de España

Fondos europeos Next Generation

1. Samia Benmansour; Cristina Pintado-Zaldo; Javier Martínez-Ponce; Antonio Hernández-Paredes; Antonio Valero-Martínez; Miriam Gómez-Benmansour; Carlos J. Gómez-García The versatility of ethylene glycol to tune the dimensionality and magnetic properties in DyIII-anilato-based single-ion magnets. Crystal Growth & Design, 2023, 1269 - 1280. ISSN: 1528-7483.

2. Soumen Kumar Dubey; Maxcimilan Patra; Kajal Gupta; Subham Bhattacharjee; Rajat Saha; Carlos J. Gómez-García A 3D Coordination Polymer Based on Syn-Anti Bridged [Mn(RCOO)₂]_n Chains Showing Spin-Canting with High Coercivity and an Ordering Temperature of 14 K. Magnetochemistry, 2023, 9, 55.

3. Richa; Akhilesh Kumar; Indresh Verma; Pankaj Garg; Rohan D. Erande; Saleem Javed; Amit Rajput; Carlos J. Gomez Garcia; Antonio J. Mota; Himanshu Arora Magnetic properties and pH-controlled reversible interconversion of μ-oxido into μ-hydroxido in oxo-carboxylato bridged iron (III) dimers: Theoretical and experimental insights. Journal of Molecular Structure, 2023, 1285, 135426.

4. Benmansour, S.; Hernández-Paredes, A.; Defez-Aznar, K.; Gómez-García, C.J. Two-Dimensional Lattices with Lanthanoids, Anilato Ligands and Formamide. Crystals 2023, 13, 939.

5. Walter Cañón-Mancisidor; Patricio Hermosilla-Ibáñez; Evgenia Spodine; Verónica Paredes-García; Carlos J. Gómez-García; Diego Venegas-Yazigi Spin Frustrated Pyrazolato Triangular CuII Complex: Structure and Magnetic Properties, an Overview. Magnetochemistry, 2023, 9, 155.

6. Vahid Mirdarvatan; Bahram Bahramian; Aliakbar Dehno Khalaji; Tereza Vaclavu; Carlos J. Gomez-García; Samia Benmansour; Smail Triki A novel mixed azido/phenoxido bridged 1D CuII coordination polymer containing o-vanillin-based compartmental ligand: Synthesis, magnetism, phenoxazinone synthase and catalytic activity in epoxidation of alkenes. Polyhedron, 2023, 244, 116581.

7. Rabi Sankar Sarkar; Carlos J. Gómez-García; Michael G. B. Drew; Shouvik Chattopadhyay Slow relaxation of the magnetization in two cobalt (III)/cobalt (II) dimers. New J. Chem., 2023, 47, 16913.

8. Rajat Saha; Kajal Gupta; Carlos J. Gómez García Strategies to Improve Electrical Conductivity in Metal-Organic Frameworks: A Comparative Study. Crystal Growth & Design, 2024, 24, 2235-2265.

9. Kajal; Richa Vinayak; Carlos J. Gómez-Garciá; Samia Benmansour; Hari Pada Nayek Quadruple bridged-carbonate supported dodecanuclear [Ni₈Ca₄] coordination cluster. New J. Chem., 2024, 48, 3239.

10. Naba Kr Mandal; Sudeshna Nandi; Samia Benmansour; Carlos J. Gómez-García; Krishnendu Acharya; Jnan Prakash Naskar Design, synthesis and structure of a trinuclear copper (II) complex having a Cu₃OH core with regard to aspects of antiproliferative activity and magnetic properties. New J. Chem., 2024, 48, 5782.

11. Sarnali Sanfui; Arya Roychowdhury; Mohammad Usman; Eugenio Garribba; Carlos J. Gómez-García; Sankar Prasad Rath Metal vs Ligand Oxidation: Coexistence of Both Metal-Centered and Ligand-Centered Oxidized Species. Inorg. Chem., 2024, 63, 5423-5431.

12. Anissa Hannachi; Youness El Bakri; Kandasamy Saravanan; Carlos J. Gomez-García; Hatem A. Abuelizz; Rashad Al-Salahi Wajda Smirani Metamagnetism and canted antiferromagnetic ordering in two monomeric Co II complexes with 1-(2-pyrimidyl)piperazine. Hirshfeld surface analysis and theoretical studies. RSC Adv., 2024, 14, 11557.

13. Biplab Biswas; Anjila I. Siddiqui; Mithun Chandra Majee; Swadhin Kumar Saha; Biswajit Mondal; Rajat Saha; Carlos J. Gómez García Heptanuclear Mixed-Valence Co₄^IIICo₃^II Molecular Wheel-A Molecular Analogue of Layered Double Hydroxides with SingleMolecule Magnet Behavior and Electrocatalytic Activity for Hydrogen Evolution Reactions. Inorg. Chem., 2024, 63, 6161-6172.

14. Samia Benmansour; Cristina Pintado-Zaldo; Sofía H. Casal-García; Javier Martínez-Ponce; Carlos J. Gómez-García Anilato-Based Coordination Polymers with Slow Relaxation of the Magnetization: Role of the Synthetic Method and Anilato Ligand. Chem. Eur. J., 2024, e202400410.

15. Samia Benmansour; Marco Segura-Andreu; Carlos J. Gomez-García Tb and Er dimers based on an asymmetric anilato ligand with slow magnetic relaxation. Inorg. Chim. Acta, 2024, 571, 122189.

16. Arka Patra; Avijit Das; Abhimanyu Sarkar; Carlos J. Gómez-García; Chittaranjan Sinha Tetranuclear NiII-Mannich base complex with oxygenase, water splitting and ferromagnetic and antiferromagnetic coupling properties. Dalton Trans., 2024, 53, 13515–13528.

17. Sarnali Sanfui; Mohammad Usman; Arya Roychowdhury; Subhadip Pramanik; Eugenio Garribba; Carlos J. Gómez García; Peter P.-Y. Chen; Sankar Prasad Rath Bridge vs Terminal Cyano-coordination in Binuclear Cobalt Porphyrin Dimers: Interplay of Electrons between Metal and Ligand and Spin-Coupling via Bridge. Inorg. Chem. 2024, 63, 15619-15633.

18. Rajat Saha; Carlos J. Gómez-García Extrinsically conducting MOFs: guest-promoted enhancement of electrical conductivity, thin film fabrication and applications. Chemical Society Reviews, 2024, 53, pp. 9490 - 9559.

Conference Contributions

Carlos J. Gómez-García; Samia Benmansour; Antonio Hernández-Paredes; Cristian Martínez-Hernández; Cristina Pintado-Zaldo; Javier Martínez-Ponce; Antonio Valero-Martínez; Miriam Gómez-Benmansour Anilato-based layered ferrimagnets and single-ion magnets. 5th International Conference on Functional Molecular Materials. FUNMAT2023, 29-31 March 2023, Cracovia, Poland, Invited Speaker at the International Congress.

Sofía H. Casal-García; Samia Benmansour; Carlos J. Gómez-García A Dy^III Layered MOF with Field-Induced Slow Relaxation of the Magnetization. 3er Workshop for Young Researchers in Chemistry, 18-19 May 2023, Valencia, Spain, Conference in International Congress.

Carlos J. Gómez-García; Samia Benmansour; Antonio Hernández-Paredes; Cristian Martínez-Hernández; Cristina Pintado-Zaldo; Javier Martínez-Ponce; Antonio Valero-Martínez; Miriam Gómez-Benmansour The use of anilato ligands to construct magnetic and conducting MOFs XXXIX REUNIÓN BIENAL DE LA SOCIEDAD ESPAÑOLA DE QUÍMICA, 25-29 June 2023, Zaragoza, Spain, Invited Speaker at the International Congress.

Carlos J. Gómez-García; Samia Benmansour; Antonio Hernández-Paredes; Cristian Martínez-Hernández; María Bayona-Andrés Post-synthetic tunning of the magnetic properties in layered magnets and single-ion magnets (SIM). Emerging Research on Molecule-Based Magnets: from Theory to Experiment. 2023 Pre-ICMM Symposium, Guangzhou, China, 7-9 Septiembre 2023, Invited Speaker at the International Congress.

Carlos J. Gómez-García; Samia Benmansour; Antonio Hernández-Paredes; Cristina Pintado-Zaldo; Sofía H. Casal-García From 0D to 2D and 3D anilato-based single-molecule and single-ion magnets. 18th International Conference on Molecule-Based Magnets - ICMM2023, Nanjing, China, 10-14 Septiembre 2023, Conference in International Congress.

Carlos J. Gómez-García; Samia Benmansour; Cristian Martínez-Hernández Multifunctional molecule-based magnets with anilato ligands. Multifunctional Molecule-Based Materials. Post-ICMM 2023 Symposium, Tianjin, China,15-17 Septiembre 2023, Invited Speaker at the International Congress.

Cristina Pintado-Zaldo; Samia Benmansour; Carlos J. Gómez-García Single Ion Magnets based on anilato and ethylene glycol. 1st European School on Advanced Materials. ESAM, 15-18 Octubre 2023, Gandía, Spain, Conference in International Congress.

Sofia H. Casal-García; Samia Benmansour; Carlos J. Gómez-García A New two-Dimensional MOF with field induced Single Ion Magnet behaviour. 1st European School on Advanced Materials. ESAM, 15-18 Octubre 2023, Gandía, Spain, Conference in International Congress.

Carlos J. Gómez-García Conducting 2D and 3D MOFs. Measurements, mechanisms and types. 1st European School on Advanced Materials. ESAM, 15-18 Octubre 2023, Gandía, Spain, Invited Speaker at the International Congress.

2024

Carlos J. Gómez-García, Samia Benmansour, Antonio Hernández-Paredes, Cristina Pintado-Zaldo, Sofía H. Casal-García, Javier Martínez-Ponce Magnetic and Conducting 2D and 3D Metal Organic Frameworks. International Conference on Natural Sciences and Engineering for Sustainable Development (NSESD2024), 6-7 Marzo 2024, Asansol, West Bengal, India, Invited Speaker at the International Congress.

Cristina Pintado-Zaldo, Louise Bureller, Javier Martínez-Ponce, Sofía H. Casal-García, Carlos J. Gómez-García, Samia Benmansour The first tris(anilato)metalate complex with a divalent cation and the first trimer with an anilato ligand. 9th European Conference on Molecular Magnetism, 14-19 July 2024, Krakow-Poland, P.52, Conference in International Congress. 

Carlos J. Gómez-García, Cristina Pintado-Zaldo, Javier Martínez-Ponce, Sofía H. CasalGarcía, Samia Benmansour Slow magnetic relaxation in layered lanthanoid-anilato lattices. 9th European Conference on Molecular Magnetism, 14-19 July 2024, Krakow-Poland, P.132, Conference in International Congress.

Sofía H. Casal-García, Gonzalo de Joz Latorre, Cristina Pintado-Zaldo, Javier MartínezPonce, Carlos J. Gómez-García, Samia Benmansour Transition metal-based magnetic heteroleptic chains with anilato and imidazole-type ligands. 9th European Conference on Molecular Magnetism, 14-19 July 2024, Krakow-Poland, P.150, Poster at International Congress.

 Cristina Pintado-Zaldo, Louise Bureller, Javier Martínez-Ponce, Sofía H. Casal-García, Carlos J. Gómez-García, Samia Benmansour The first tris(anilato)metalate complex with a divalent cation and the first trimer with an anilato ligand. 9th European Conference on Molecular Magnetism, 14-19 July 2024, Krakow-Poland, P.162, Poster at International Congress.

Samia Benmansour, Javier Martínez-Ponce, Marco Segura-Andreu, Cristina Pintado-Zaldo, Sofía H. Casal-García, Carlos J. Gómez-García Slow relaxation of the magnetization in lanthanoid dimers with an asymmetric anilato ligand. 9th European Conference on Molecular Magnetism, 14-19 July 2024, Krakow-Poland, P.186, Poster at International Congress.

Samia Benmansour, Carlos J. Gómez García, Antonio Hernandez Paredes Reversible solvents exchange in layered MOFs with slow relaxation of the magnetization. 3rd Asian Conference on Molecular Magnetism, 1 – 4 September 2024, Busan, Republic of Korea, Conference in International Congress.

Carlos J. Gómez García, Samia Benmansour, Cristian Martínez-Hernández Ferrimagnetic order in layered anilato-based heterometallic lattices. 3rd Asian Conference on Molecular Magnetism, 1 – 4 September 2024, Busan, Republic of Korea, Invited Speaker at the International Congress.

Ph.D. Thesis, Degree Thesis and Research Reports

Carmen Llopis Borrego Síntesis de redes extendidas de lantanoides y ligandos anilato en medio acuoso. Faculty of Chemistry, University of Valencia, Valencia, 2022, Bachelor's thesis.

Marco Segura Andreu Síntesis y caracterización de redes magnéticas porosas con lantanoides y ligandos de tipo anilato asimétricos. Faculty of Chemistry, University of Valencia, Valencia, 2022, Bachelor's thesis.

Cristina Pintado Zaldo Síntesis y caracterización de redes metal-orgánicas (MOF) con propiedades de imanes mono-moleculares (SMM). Faculty of Chemistry, University of Valencia, Valencia, 2022, Master's thesis.

Celso Iniesta Martín Desarrollo de nuevas estrategias para la idenficación y cuantificación de escopolamina en bebidas alcohólicas y no alcohólicas. Faculty of Chemistry, University of Valencia, Valencia, 2023, Bachelor's thesis.

Cristian Martínez Hernández Sensores magnéticos basados en polímeros de coordinación porosos con ordenamiento magnético. Faculty of Chemistry, University of Valencia, Valencia, 2023, Ph.D. thesis.

Gonzalo de Joz Latorre Transition metal-based metal-organic frameworks with anilato ligands. Faculty of Chemistry, University of Valencia, Valencia, 2024, Bachelor's thesis.

Antonio Hernández Paredes Redes metal-orgánicas magnéticas con relajación lenta de la magnetización basadas en ligandos anilatos. Faculty of Chemistry, University of Valencia, Valencia, 2024, Ph.D. thesis.

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