Martyn Pillinger

Academic qualifications

1994: PhD Chemistry in the group of Professor John Evans, University of Southampton, England - "EXAFS studies of polyoxometalates and polyoxometalate-anion-pillared layered double hydroxides"
1990: BSc Chemistry (Class 1), University of Southampton, England

Previous activities

2008-2015: Research Assistant at CICECO
2007-2008: Research Assistant at the Instituto de Engenharia Electrónica e Telemática de Aveiro, Aveiro, Portugal
2002-2007: Research Assistant at CICECO
1999-2002: Post-doc researcher in the group of Prof. Dr. João Rocha, Department of Chemistry, University of Aveiro (UA), Portugal (UA and FCT grants)
1996-1999: Post-doc researcher in the group of Prof. Alan Dyer, Chemistry Division, Science Research Institute, Universidade de Salford, England (EU Framework 4 Nuclear Fission Safety Program - Partitioning Experiments and Waste Minimisation - "Waste Volume Minimisation Using Highly Selective Inorganic Ion Exchange Materials")
1994-1995: Post-doc researcher in the group of Prof. Dr. Carlos C. Romão, Instituto de Tecnologia Química e Biológica, Oeiras, Portugal (TMR Programme - Selective Processes and Catalysis Involving Small Molecules - "Syntheses and Chemistry of Organotransition Metal Oxides")

Martyn’s research mainly involves the synthesis and chemistry of inorganic/organometallic hybrid and composite materials with interesting photofunctional, biofunctional and/or catalytic properties. A recurring theme has been organometallic inclusion and intercalation chemistry employing, for example, ordered mesoporous materials, cyclodextrins and layered double hydroxides as hosts (some examples are given on this page). To fully understand these systems it has been crucial to use multiple analysis techniques, e.g. X-ray absorption spectroscopy and powder X-ray diffraction. These studies have been and continue to be performed in close collaboration with colleagues at CICECO and other Portuguese institutions. Other collaborative research interests include the synthesis and characterization of molecular and hybrid molybdenum oxide-based catalysts for oxidation reactions, and solid acid catalysts for biomass conversion.

Present

PhD students: Isabel Margarida Bento Calhau (FCT grant; cosupervision with Isabel S. Gonçalves), Rodrigo Pinto Monteiro (FCT grant; cosupervision with Isabel S. Gonçalves), Martinique da Silva Nunes (FCT grant; cosupervision with Isabel S. Gonçalves and Anabela A. Valente).

Previous

PhD students (leading to thesis): Ana Sofia Vagueiro de Sousa Dias (2007, cosupervision with Anabela A. Valente), Bernardo Ramos Batista Monteiro (2009, cosupervision with Isabel S. Gonçalves), Maria Margarida Feitor Pintão Moreno Antunes (2012, cosupervision with Anabela A. Valente).
MSc students (leading to thesis): Joana Leão Candeias (2012, cosupervision with Anabela A. Valente), Joana Helena Aguiar de Almeida Pinho Abrantes (2014, cosupervision with Anabela A. Valente), Clara Isabel Ribeiro Magalhães (2015, cosupervision with Isabel S. Gonçalves).
Post-docs: Ana Sofia Madureira Bruno (2009-2015, cosupervision with Anabela A. Valente), Sérgio Nuno Martins Lima (2005-2012, cosupervision with Anabela A. Valente), Sandra Maria Nunes Gago (2006-2010), Ana Catarina Costa Gomes (2010-2019, cosupervision with Isabel S. Gonçalves), Carlos Granadeiro (2016-2018, cosupervision with Salete S. Balula (University of Porto)), Margarida Antunes (2013-2019, cosupervision with Anabela A. Valente).

Aveiro (CICECO): Isabel S. Gonçalves, Anabela A. Valente, Ana C. Gomes, Patrícia Neves, Sofia M. Bruno, Margarida M. Antunes, Filipe A. Almeida Paz.
Portugal: Carlos C. Romão (ITQB), André D. Lopes (University of the Algarve), Prof. Sérgio Seixas de Melo (University of Coimbra), Salete Balula and Luís Cunha Silva (University of Porto).

Coordinator of the project SASCOT "Stimuli-activated systems for carbon monoxide therapy" (CENTRO-01-0145-FEDER-028031; 1/5/2018-30/4/2022).

Participant in the project HyLight "Rational Design of High Efficiency and Stability Organic-Inorganic Hybrid White Light Emitters" (Lead Institution = University of Coimbra; POCI-01-0145-FEDER-031625; 1/7/2018-30/6/2022).
Participant in the project BiOle_AcidOxCat "Catalytic conversion of biomass-derived olefins" (Lead Institution = Universidade de Aveiro; POCI-01-0145-FEDER-030075; 26/7/2018-25/3/2022).

PTDC/QEQ-SUP/1906/2012 (team member; principal contractor = University of Aveiro): Use of molecular containers to modify metallocene-based catalysts
PTDC/EQU-EQU/121677/2010 (team member; principal contractor = Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares - Porto): Desulfurization of fuels using green heterogeneous oxidative catalytic processes
CICECO-funded project (1/3/10-28/2/11, principal investigator): "Metal carbonyl intercalated anion exchangers as drug delivery systems"
PTDC/QUI/71198/2006 (participant): "Ansa-bridged Organorhenium(VII) oxides and their application as homogeneous and heterogeneous catalysts"
POCI/CTM/58507/2004 (principal investigator): "Multifunctional anionic clays"
POCI/QUI/56109/2004 (participant): "New oxometal compounds with tailored catalytic properties"
POCI/QUI/56112/2004 (participant): " Catalytic conversion of carbohydrates into furan derivatives"
POCTI/QUI/37990/2001 (participant): "Tailored oxomolybdenum catalysts"
POCTI/QUI/32889/99 (participant): "Heterogenisation of photochemically and catalytically active transition metal complexes on mesoporous oxides"

260 papers in international peer-reviewed journals, w-index 11, h-index 53

Top three cited papers (December 2023):
(233 citations) Octahedral Bipyridine and Bipyrimidine Dioxomolybdenum(VI) Complexes: Characterization, Application in Catalytic Epoxidation, and Density Functional Mechanistic Study, F. E. Kühn, M. Groarke, É. Bencze, E. Herdtweck, A. Prazeres, A. M. Santos, M. J. Calhorda, C. C. Romão, I. S. Gonçalves, A. D. Lopes, M. Pillinger, Chem. Eur. J., 2002, 8, 2370. Link
(284 citations) Dehydration of xylose into furfural over micro-mesoporous sulfonic acid catalysts, A.S. Dias, M. Pillinger, A.A. Valente, J. Catal., 2005, 229, 414. Link
(206 citations) Conversion of mono/di/polysaccharides into furan compounds using 1-alkyl-3-methylimidazolium ionic liquids, S. Lima, P. Neves, M. M. Antunes, M. Pillinger, N. Ignatyev, A. A. Valente, Appl. Catal. A: Gen., 2009, 363, 93-99. Link

Reviews
1) Group 6 carbonyl complexes of N,O,P-ligands as precursors of high-valent metal-oxo catalysts for olefin epoxidation, S.M. Bruno, A.A. Valente, I.S. Gonçalves, M. Pillinger, Coord. Chem. Rev., 2023, 478, 214983. Link
2) Reaction induced self-separating metal catalysts – Wonder systems in 21st century catalysis, P. Neves, D.M. Gomes, I.S. Gonçalves, M. Pillinger, A.A. Valente, Coord. Chem. Rev., 2023, 491, 215229. Link

Carbon monoxide-releasing materials
This research theme comprises the design of metal carbonyl complexes as prodrugs for carbon monoxide (CO) delivery for therapeutic applications in human medicine (e.g., as antimicrobial agents to fight drug-resistant bacteria). We aim to develop pharmaceutically acceptable CO-releasing materials based on macromolecular (e.g., cyclodextrins, cucurbiturils) and metal-organic nanomaterial scaffolds.
1) A.F. Silva, I.B. Calhau, A.C. Gomes, A.A. Valente, I.S. Gonçalves, M. Pillinger, A hafnium-based metal-organic framework for the entrapment of molybdenum hexacarbonyl and the light-responsive release of the gasotransmitter carbon monoxide, Mater. Sci. Eng. C, 2021, 124, 112053. Link
2) A. F. Silva, I. B. Calhau, A. C. Gomes, A. A. Valente, I S. Gonçalves, M. Pillinger, Tricarbonyl-Pyrazine-Molybdenum(0) Metal−Organic Frameworks for the Storage and Delivery of Biologically Active Carbon Monoxide, ACS Biomater. Sci. Eng., 2023, 9, 1909−1918. Link

1) An Indigo Carmine-Based Hybrid Nanocomposite with Supramolecular Control of Dye Aggregation and Photobehavior, A.L. Costa, A.C. Gomes, M. Pillinger, I.S. Gonçalves, J.S. Seixas de Melo, Chem. Eur. J., 2015, DOI: 10.1002/chem.201501344. Link

Tune into the blues: Zn-Al layered double hydroxides (LDHs) containing solely indigo carmine (IC) or 1-hexanesulfonate (HS) anions, or a mixture of the two with different HS/IC molar ratios, were prepared by the direct synthesis method. For the LDH containing solely IC anions, the dye molecules assembled within the interlayer galleries to form a J-type stacking arrangement. Through a comprehensive electronic spectral and photophysical study it was shown that incorporation of IC within the LDH decreased the level of aggregation, and that further addition of HS induced the appearance of isolated IC units within the LDH galleries. The indigo carmine-based nanocomposites constitute a step-forward in the design of hybrid materials with tunable properties.

2) Controlling the Fluorescence Behavior of 1-Pyrenesulfonate by Cointercalation with a Surfactant in a Layered Double Hydroxide, A.L. Costa, A.C. Gomes, M. Pillinger, I.S. Gonçalves, J.S. Seixas de Melo, Langmuir, 2015, 31, 4769. Link

3) Intercalation of a Molybdenum η³-Allyl Dicarbonyl Complex in a Layered Double Hydroxide and Catalytic Performance in Olefin Epoxidation, A. C. Gomes, S. M. Bruno, C. A. Gamelas, A. A. Valente, M. Abrantes, I. S. Gonçalves, C. C. Romão, M. Pillinger, Dalton Trans, 2013, 42, 8231. Link

4) Intercalation of a Molybdenum(0)-Tetracarbonyl-Bipyridine Complex in a Layered Double Hydroxide, A. C. Gomes, S. M. Bruno, A. A. Valente, I. S. Gonçalves, M. Pillinger, J. Organomet. Chem., 2013, 744, 53. Link
5) Preparation and photophysical characterisation of Zn-Al layered double hydroxides intercalated by anionic pyrene derivatives, S. Gago, T. Costa, J. Seixas de Melo, I. S. Gonçalves, M. Pillinger, J. Mater. Chem., 2008, 18, 894. Link

6) Investigation of layered double hydroxides intercalated by oxomolybdenum catecholate complexes, B. Monteiro, S. Gago, F. A. Almeida Paz, R. Bilsborrow, I. S. Gonçalves, M. Pillinger, Inorg. Chem., 2008, 47, 8674. Link
7) Immobilization of Oxomolybdenum Species in a Layered Double Hydroxide Pillared by 2,2'-Bipyridine-5,5'-Dicarboxylate Anions, S. Gago, M. Pillinger, A. A. Valente, T. M. Santos, J. Rocha, I. S. Gonçalves, Inorg. Chem., 2004, 43, 5422. Link

8) Immobilization of Lanthanide Ions in a Pillared Layered Double Hydroxide, S. Gago, M. Pillinger, R. A. Sá Ferreira, L. D. Carlos, T. M. Santos, I. S. Gonçalves, Chem. Mater., 2005, 17, 5803. Link
Other publications

1) Desulfurization of model diesel by extraction/oxidation using a zinc-substituted polyoxometalate as catalyst under homogeneous and heterogeneous (MIL-101(Cr) encapsulated) conditions, D. Julião, A.C. Gomes, M. Pillinger, L. Cunha-Silva, B. de Castro, I.S. Gonçalves, S.S. Balula, Fuel Processing Technology, 2015, 131, 78. Link

2) Investigation of a dichlorodioxomolybdenum(VI)-pyrazolylpyridine complex and a hybrid derivative as catalysts in olefin epoxidation, T.R. Amarante, P. Neves, F.A.A. Paz, A.A. Valente, M. Pillinger, I.S. Gonçalves, Dalton Trans., 2014, 43, 6059. Link

3) Hydrothermal Synthesis, Crystal Structure and Catalytic Potential of a One-Dimensional Molybdenum Oxide/Bipyridinedicarboxylate Hybrid, T. R. Amarante, P. Neves, A. A. Valente, F. A. A. Paz, A. N. Fitch, M. Pillinger, I. S. Gonçalves, Inorg. Chem., 2013, 52, 4618. Link

4) Catalytic Cyclodehydration of Xylose to Furfural in the Presence of Zeolite H-Beta and a Micro/Mesoporous Beta/TUD-1 Composite Material, S. Lima, M. M. Antunes, A. Fernandes, M. Pillinger, M. F. Ribeiro, A. A. Valente, Appl. Catal. A: Gen., 2010, 388, 141. Link

5) Grafting of molecularly ordered mesoporous phenylene-silica with molybdenum carbonyl complexes: Efficient heterogeneous catalysts for the epoxidation of olefins, A. C. Coelho, S. S. Balula, S. M. Bruno, J. C. Alonso, N. Bion, P. Ferreira, M. Pillinger, A. A. Valente, J. Rocha, I. S. Gonçalves, Adv. Synth. Catal., 2010, 352, 1759. Link

6) Investigation of molybdenum tetracarbonyl complexes as precursors to Mo^VI catalysts for the epoxidation of olefins, T. R. Amarante, P. Neves, A. C. Coelho, S. Gago, A. A. Valente, F. A. A. Paz, M. Pillinger, I. S. Gonçalves, Organometallics, 2010, 29, 883. Link

7) Influence of Cyclodextrins on Catalytic Olefin Epoxidation with Metal Carbonyl Compounds. Crystal Structure of the TRIMEB Complex with CpFe(CO)₂Cl, S. S. Balula, A. C. Coelho, S. S. Braga, A. Hazell, A. A. Valente, M. Pillinger, J. D. Seixas, C. C. Romão, I. S. Gonçalves, Organometallics, 2007, 26, 6857. Link

8) Immobilisation of rhodium acetonitrile complexes in ordered mesoporous silica, M. Pillinger, C. D. Nunes, P. D. Vaz, A. A. Valente, I. S. Gonçalves, P. J. A. Ribeiro-Claro, J. Rocha, L. D. Carlos, F. E. Kühn, Phys. Chem. Chem. Phys., 2002, 4, 3098. Link

9) Sorption behaviour of radionuclides on crystalline synthetic tunnel manganese oxides, A. Dyer, M. Pillinger, J. A. Newton, R. Harjula, T. Möller, S. Amin, Chem. Mater., 2000, 12, 3798. Link

10) Ion exchange of caesium and strontium on a titanosilicate analogue of the mineral pharmacosiderite, A. Dyer, M. Pillinger, S. Amin, J. Mater. Chem., 1999, 9, 2481. Link