Paulo Nuno Martinho

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    Ongoing Project


  • Electrostatic Induced Control of Magnetic Molecules for Spintronics


  • Spintronics

        Binary data storage operates by switching between two states which are both stable under the same ambient conditions. In the last 10 years a new model of spin-based electronics (spintronics) has emerged, where the goal is to store binary information via the orientation of individual electron spins. Magnetic compounds with good potential for incorporation into spintronic materials include spin crossover (SCO) transition metal complexes. These molecules can switch between two magnetic states with a simple stimulus such as heat, pressure, light or magnetic field, and the switch is often accompanied by a considerable hysteretic window. Research has been developed where bistable magnetic states are addressed mainly by application of temperature or light but for electronic purposes, it is desirable to apply an electric field to switch between magnetic states permitting the fabrication of molecular devices where states are controlled electrically. This ongoing project wishes to exploit the fact that magnetic molecules can switch between magnetic states by application of an external electric field. The project is dedicated to the synthesis of both mononuclear and dinuclear magnetic molecules, the investigation of electrostatic spin crossover active molecules, their assembly into nano-objects and the incorporation of these active molecules and nano-objects into devices.




  • Modified electrodes based on binuclear metal complexes for electrocatalysis


  • Electrocatalysis

     The development of modified electrodes with conducting polymers containing first row transition metals has been a very active area of research in recent years, especially because the metal centres are incorporated along the polymer backbone. Several applications have been reported such as electrocatalysis, sensors and optical devices, among others. A common strategy for electrochemical synthesis of metal-containing polymers is to attach polymerisable groups (aniline, pyrrole, etc.) onto metal complexes. Salphen-type polymers are attractive, because extra synthetic steps can be avoided once Schiff base complexes can be conveniently electropolymerised. Among monomers, bis(metallo)salphen are of special interest for electropolymerisation. They behave as two connected independent salphen units with possibility to fine tune each salphen with desirable properties. Synthesis of asymmetric bis-salphen complexes permits the introduction of functional groups with different properties and variation of the metal centres gives distinct redox behaviour.
    This ongoing project wishes to synthesise symmetric and asymmetric bis-salphen complexes by reaction of 3,3'-diaminobenzidine with salicylaldehydes with different substituents. The dinuclear complexes are electropolymerised on an inert substrate by a potentiodynamic mode and their films characterised and the performance of the modified electrodes towards the electrocatalytic conversion of O2 investigated.




  • Smart polymer switches for green CO2 capture


  • Polymer Switches

     Hydrocarbon fuels are currently the most important source of energy because of their ready availability, stability, and high energy density. Unfortunately, combustion of this source of energy carries a significant issue to the environment and environmental pollution, for which carbon dioxide emissions are responsible. The increasing atmospheric concentration of CO2 has been predicted by models which suggest dramatic and irreversible changes if actions are not urgently taken. It is now well established that CO2 may be sequestered and stored as liquid CO2 or solid carbonate but both procedures solutions are energetically demanding and financially costly. This project explores the fixation chemistry of CO2 by exploiting potential new catalysts to both sequester and activate CO2 for further reaction.



    CV

  • 2002 - Licenciatura in Technological Chemistry, Faculdade de Ciências, Universidade de Lisboa (Portugal)


  • 2006 - Licenciatura in Teaching Physics and Chemistry, Faculdade de Ciências, Universidade de Lisboa (Portugal)


  • 2010 - PhD in Chemistry, University College Dublin (Ireland)


  • 2011 - 2012 - Guest Scientist at Karlsruhe Institute of Technology (Germany)


  • 2012 - to date - Postdoctoral Fellow at CQB, FCUL




  • Book Chapters

  • P. N. Martinho, C. Rajnak, and M. Ruben, (2013) "Nanoparticles, Thin Films and Surface Patterns from Spin-Crossover Materials and Electrical Spin State Control, in Spin-Crossover Materials: Properties and Applications" (ed M. A. HALCROW), John Wiley & Sons Ltd, Oxford, UK.


  • Publications

  • 11) E. J. Devid, P. N. Martinho, M. V. Kamalakar, Ú. Prendergast, C. Kübel, T. Lemma, J.-F. Dayen, T. E. Keyes, B. Doudin, M. Ruben, S. J. van der Molen, "The influence of molecular mobility on the properties of gold nanoparticle organic ligand networks", Beilstein J. Nanotechnol., 2014, in print.


  • 10) J. Kitchen, P. N. Martinho, G. G. Morgan. T. Gunnlaugsson, "Synthesis, crystal structure and EPR spectroscopic analysis of novel copper complexes formed from N-pyridyl-4-nitro-1,8-naphthalimide ligands", Dalton Trans, 2014, 43, 6468-6479.


  • 9) P. N. Martinho, A. I. Vicente, S. Realista, M. S. Saraiva, A. I. Melato, L. P. Ferreira, M. D. Carvalho, "Solution and solid state properties of Fe(III) complexes bearing N-ethyl-N-(2-aminoethyl)salicylaldiminate ligands", J. Organomet. Chem., 2014, 760, 48-54.


  • 8) P. N. Martinho, B. Gildea, M. M. Harris, T. Lemma, A. D. Naik, H. Möller-Bunz, T. E. Keyes, Y. Garcia, G. G. Morgan, "Cooperative spin transition in a mononuclear Mn(III) complex", Angew. Chem. Int. Ed., 2012, 51, 11995-11999.


  • 7) P. N. Martinho, T. Lemma, G. Picardi, B. Gildea, R. J. Forster, T. E.Keyes, G. Redmond, G. G. Morgan, "Template assembly of spin crossover 1D nanowires", Angew. Chem. Int. Ed., 2012, 51, 12597-12601.


  • 6) P. N. Martinho, Y. Ortin, B. Gildea, C. Gandolfi, G. McKerr, B. O'Hagan, Martin Albrecht, G. G. Morgan, "Inducing Hysteretic Spin Crossover in Solution", Dalton Trans., 2012, 41, 7461-7463.


  • 5) C. Gandolfi, T. Cotting, P. N. Martinho, V. K. Malik, C. Bernhard, O. Sereda, A. Neels, G. G. Morgan, M. Albrecht, "Synthesis and self-assembly of spin-labile and redox-active manganese(III) complexes", Dalton Trans., 2011, 40, 1855-1865.


  • 4) C. Gandolfi, N. Miyashita, D. Kurth, P. N. Martinho, G. G. Morgan, M. Albrecht, "Organization of potentially spin- and redox-labile metal centers into Langmuir and Langmuir-Blodgett films", Dalton Trans., 2010, 39, 4508-4516.


  • 3) P. N. Martinho, C. J. Harding, H. Möller-Bunz, M. Albrecht, G. G. Morgan "Inducing spin crossover in Fe(III) amphiphiles", Eur. J. Inorg. Chem., 2010, 675-679.


  • 2) P. N. Martinho, S. Quintal, P. J. Costa, S. Losi, V. Félix, C. Gimeno, M. G. B. Drew, P. Zanello, M. J. Calhorda, "New polynuclear Mo-Fe complexes with benzimidazole ligands", Eur. J. Inorg. Chem., 2006, 20, 4096-4103.


  • 1) M. J. Calhorda, P. J. Costa, P. N. Martinho, M. C. Gimeno, A. Laguna, S. Quintal, M. D. Villacampa, "Synthesis and ligand properties towards gold and silver of the ferrocenylamidobenzimidazole ligand", J. Organomet. Chem., 2006, 691, 20, 4181-4188.



  • Research Projects


  • Sponsor: Fundação Calouste Gulbenkian
    Title: Smart polymer switches for green CO2 capture.
    Start Date / End Date: 01-Jan-2014 / 31-Dec-2014


  • Sponsor: CMST COST Action CM1305 (Management Committee)
    Title: Explicit Control Over Spin-states in Technology and Biochemistry (ECOSTBio)
    Start Date / End Date: 28-Jan-2014 / 14-Nov-2017