RESEARCH GROUP
Supramolecular Organometallic and Main Group Chemistry Laboratory

Research Interests

Welcome to our Research Group. We are a highly motivated team working towards two main research streams. On one side, the development and understanding of the chemistry of confined supramolecular organometallic systems, and on the other side, the study of low-valent main group organometallics systems’ reactivity and their bonding to transition metals. Both research avenues respond to the same call, finding molecular and supramolecular catalytic systems to activate “inert” molecules. In particular, the activation of CO2 is of interest to this research team because of its environmental implications to the chemical and energy industries in developing a sustainable way to transform energy with cero carbon emissions.The control of reactivity, selectivity, and stability at an active catalytic site is often achieved by tuning the catalytic metal first coordination sphere. However, an alternative and powerful way to make a better stereo-control is tailoring the secondary coordination sphere by employing well-defined and discrete host cavities as reaction nanovessels.The encapsulation of organometallic catalytic systems allows access to unique reaction microenvironments that drastically influence the course of catalytic reactions, in a way that the non-encapsulated free catalyst can outcompete. Both the catalyst and host cavity control the catalytic properties of the confined system. This dual-manifold allows fine-tuning for kinetic stabilisation, creating a unique confined chemical space and giving access to better catalyst stability, novel selectivity, and accelerating the reaction rate. Many of these catalyst features remark their relevance to the operation of enzymatic catalysis.
 

 

Our motivation is to use our findings in confined and main group chemistry to advance chemical research and catalysis while promoting sustainability.

FUNDING

We thank the EU, the Spanish Ministry of Science, Innovation and Universities, the Government of Andalusia, the University of Huelva and AIQBE (Asociación de Industrias Químicas, Básicas y Energéticas de Huelva) for financial support.

Reversible Redox Ligand-Centered Reactivity in 2,6-Bisiminopyridine Aluminum Systems. J. M. Delgado-Collado, H. Videa, P. J. Serrano-Laguna, M. Ángeles Fuentes, E. Álvarez, A. Díaz Quintana, A. J. Martínez-Martínez,* A. Rodríguez-Delgado,* J. Cámpora* Inorg. Chem., 2024, 63, 41, 19156–19166. DOI: https://doi.org/10.1021/acs.inorgchem.4c02664

Synthesis, Characterization, and Photochemistry of a Ga₂L₃ Coordination Cage with Dithienylethene-Catecholate Ligands. A. Carbonell, I. Izquierdo, D. B. Guzmán Ríos, G. Norjmaa, G. Ujaque, A. J Martínez-Martínez* and Uwe Pischel* Inorg. Chem., 2024, 63, 42, 19872–19884. DOI: https://doi.org/10.1021/acs.inorgchem.4c03279

Revealing unbound β-diketiminate anions: structural dynamics from caesium complexes. H. Videa, A. J. Martínez-Martínez* Dalton Trans., 2023, 52, 13058-13062. DOI: https://doi.org/10.1039/D3DT01592K

Highlighted as a Front Cover.

Contacted” vs “separated” aluminyls: Dynamic alkali metal effects in H2 activation. Videa, Hellen; Martínez-Martínez, Antonio J. ChemRxiv 2022, pre-print, DOI: chemrxiv-2022-wjs4l-v2.

Solid/Gas Reactivity of Organometallic Species in Confined Spaces. Book Chapter in Monographs in Supramolecular Chemistry, Eds. G. Lloyd and R. S Forgan. Print ISSN: 1368-8642. Series ISSN: 1368-8642. Reactivity in Confined Spaces RSC, 2021, pp. 282-321. DOI: 10.1039/9781788019705-00282

Selective mono- and dimetallation of a group 3 sandwich complex. Martínez-Martínez, Antonio J.; Kennedy, A. R.; Paprocki, V.; Fantuzzi, F.; Dewhurst, R. D.; O’Hara, C. T.; Braunschweig, H.; Mulvey, R. E. Chem. Commun.2019, 55, 9677-9680.

Directed ortho-meta’- and meta-meta’-dimetalations: A template base approach to deprotonation. Martínez-Martínez, A. J.; Kennedy, A. R.; Mulvey, R. E.; O’Hara, C. T. Science2014, 346, 834-837.

Highlighted in:

Directed Metalation. Not just for ortho. Nature Chem.2015, 7, 8.
Method aids arenemeta substitution. C&EN News2014, 92, 35.
Paper of the month: Synfacts2015, 11, 0183.

Templated deprotonative metalation of polyaryl systems: Facile access to simple, previously inaccessible multi-iodoarenes. Martínez-Martínez, A. J.; Justice, S.; Fleming, B. J. ; Kennedy, A. R.; Oswald, I. ; O’Hara, C. T.* Sci. Adv.2017, 3, e1700832.

Reversible Encapsulation of Xenon and CH2Cl2 in a Solid‐State Molecular Organometallic Framework (Guest@SMOM). Martínez-Martínez, Antonio J.; Rees, N.; Weller, A. S. Angew. Chem. Int. Ed.2019, 58, 16873-16877.

Solvent-free anhydrous Li+, Na+ and K+ salts of [B(3,5-(CF3)2C6H3)4]−, [BArF4]−. Improved synthesis and solid-state structures. Martínez-Martínez, A. J. and Weller, A. Dalton Trans.2019, 48, 3551.

Modulation of σ-Alkane Interactions in [Rh(L2)(alkane)]+ Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to η2,η2-σ-Alkane Rh(I), η1-σ-Alkane Rh(III) Complexes, and Alkane Encapsulation. Martínez-Martínez, A. J.; Tegner, B.; McKay, A.; Bukvic, A.; Rees, N.; Tizzard, G.; Coles, S.; Warren, M.; Macgregor, S.; Weller, A. J. Am. Chem. Soc. 2018, 140, 14958–14970.

MEMBERS

Mª. Ángeles Fuentes
Postdoctoral Researcher
+34959219970
mangeles.fuentes@ciqso.uhu.es

Degree in Chemistry – Universidad de Huelva (2009)
Master in Chemistry – Universidad de Huelva (2011)
PhD in Chemistry – Universidad de Huelva (2013)
Postdoctoral researcher, University of Strathclyde, UK, Prof Robert E. Mulvey, 2014–2017
Postdoctoral researcher, University of Oxford, UK, Prof Simon Aldridge, 2017–2019
Juan de la Cierva Incorporación Postdoctoral Researcher, Universidad de Huelva, Spain, Prof. Pedro J. Pérez, 2019–2021

Hellen Videa Dubón
PhD student
+34959219972
hellen.videa@ciqso.uhu.es

Degree in Chemistry – Universidad de Barcelona (2018)
Master in Chemistry – University of Barcelona (2019)
Predoctoral Student – University of Huelva (2019-present)

Ignacio Izquierdo Sánchez
PhD student
+34959219972
ignacio.izquierdo@ciqso.uhu.es

Degree in Chemistry – Universidad de Salamanca (2018)
Master in Supramolecular Chemistry – University of Salamanca (2019)
Predoctoral Student – University of Huelva (2021-present)

Adrian Carbonell Gil
PhD Student (joint with SIFO Lab)
+34 959 219 487
adrian.carbonell@ciqso.uhu.es

Diploma in Chemistry – Universidad de Huelva (2019)
Master in Applied Chemistry – University of Huelva (2021)
Predoctoral Student – University of Huelva (2020-present)

Pablo J. Serrano Laguna
PhD Student
+34 959 219 487
pabloj.serrano@ciqso.uhu.es

Diploma in Chemistry – University of Castilla-La Mancha (2018)
Master in Pharmaceutical Discovery – CEU San Pablo/Complutense/Alcalá (2019)
Predoctoral Student – University of Huelva (2022-present)

Group Leader – Contact Details:

Center for Research in Sustainable Chemistry CIQSO and Department of Chemistry
Robert H. Grubbs Building, Campus El Carmen
University of Huelva, 21007 Huelva, Spain
Tel:. +34 959 21 9909
Email: antonio.martinez@ciqso.uhu.es

Educational Background

BSc Chemistry, Universidad de Murcia, Spain, 2005
Ph.D. Chemistry (European Mention), University of Murcia, Spain, 2012
Ph.D. Advisors: Prof J. Vicente and Prof M. T. Chicote
PhD visiting fellow, University of Glasgow, UK, Prof J. E. McGrady, 2008 and 2009
Postdoctoral researcher, University of Strathclyde, UK, Dr C. O’Hara and Prof R. Mulvey, 2012–2016
Postdoctoral researcher, University of Oxford, UK, Prof Andrew Weller and SCG Chemicals Ltd-Oxford CoE, 2017–2019
Group Leader and Ramón y Cajal Researcher, University of Huelva, Spain, 2019–present

Awards/Recognitions/Fellowships

2021/22 Certification of Research Activity in the I3 Programme (Programa I3)
2019 Ramón y Cajal Research Fellowship (RYC-2017-21783)
2015 SusChem RSEQ Postdoctoral Prize best publication and scientific profile
2012 PhD Prize for the Best Thesis in Chemistry at the University of Murcia
2006 FPU Spanish Ministry of Science PhD Fellowship

Professional and University Appointments

Associated Investigator, NordCO2, Nordic Consortium for CO2 Conversion, since 2020

Membership in Professional Societies

The Spanish Royal Society of Chemistry (RSEQ)
Organometallic Chemistry Group (GEQO) and Young Chemistry Researchers (JIQ)
The Royal Society of Chemistry (RSC)
American Chemical Society (ACS)
American Association for the Advancement of Science (AAAS).

Biographical Sketch

Dr Martínez was born in Murcia, Spain, in 1981. He completed the BSc degree in Chemistry at the University of Murcia in 2015, where he also did his PhD supervised by Prof José Vicente and M. T. Chicote in organopalladium chemistry in 2012. During this period, he also worked with Prof John McGrady at the University of Glasgow (UK) studying computational organometallic chemistry. From 2012–2016, he worked with Dr Charles O’Hara and Prof Robert Mulvey at the University of Strathclyde (UK) in template main group supramolecular chemistry, and the synergistic co-operation effects in bimetallic main group systems to influence the regio-selectivity of organic reactions. From 2017–2019, worked at the University of Oxford in solid-gas catalysis using the encapsulation of transition metal catalysts in non-covalent organometallic frameworks towards the valorisation of light hydrocarbons with Prof Andrew Weller, in partnership with SCG Chemicals Ltd, one of the largest integrated petrochemical industries in Asia.

He initiated independent research as a Ramón y Cajal Researcher at the University of Huelva and the Research Center CIQSO in 2019, and currently, he is leading a young and dynamic research group.