10th Early Stage Researchers Workshop in Nanoscience

Title: Controlled synthesis of hybrid functional nanoparticles exhibiting dynamic properties

Abstract:

Hybrid nanoparticles, formed by nano-crystalline phases of different nature and combining multiple functionalities, is a fertile field of study in nanochemistry with applications in diverse areas as nanomedicine, catalysis and electronic devices.^[1] These hybrid nanostructures overcome the limits of single-component nanoparticles offering ample opportunities to tune the functionalities by rational selection of the chemical nature of the components and specifically by controlling the size and shape.

In this seminar, we will cover different approaches to obtain hybrid functional materials based on nanoparticles.

1. We will show examples of hybrid nanoparticles based on a core-shell configuration combining plasmonic metal core and different functional shells with dynamic properties such as switchable magnetic coordination polymers or flexible Metal-Organic Frameworks (MOFs).^{[1, 2]}

2. We will address the advantages of obtaining hybrid 2D-heterstructures with responsive nanoparticles capable of tuning the physical properties.

3. Finally, we will cover the preparation of enzymes@MOFs porous nanocomposites.^[3]

Figure 1. (a) HR-TEM image of Au@spin-crossover nanoparticles. (b) Spectra of Au and Au@spin-crossover nanoparticles in the visible region. (c) I–V curves of the high-conductive (purple) and low-conductive (orange) behaviours associated to the LS and HS states, respectively. Inset: Thermal variation of the electrical current for an applied voltage of 2 V in the heating and cooling modes at 1 K·min⁻¹.

References

[1] R. Torres-Cavanilles, R. Sanchis-Gual, J. Dugay, M. Coronado-Puchau, M. Giménez-Marqués, E. Coronado, Adv. Mater., 2019, 31, 1900039.

[2] (a) J. Dugay, M. Giménez-Marqués, T. Kozlova, H. Zandbergen, E. Coronado, H. S. J. van der Zant, Adv. Mater. 2015, 27, 1288. (b) A. Holovchenko, J. Dugay, M. Giménez-Marqués, R. Torres-Cavanillas, E. Coronado, H. S. J. van der Zant, Adv. Mater. 2016, 28, 7228. (c) J. Dugay, M. Aarts, M. Giménez-Marqués, T. Kozlova, H. W. Zandbergen, E. Coronado, H. S. J. van der Zant, Nano Lett. 2017, 17, 186.

[3] (a) M. Giménez-Marqués, T. Hidalgo, C. Serre and P. Horcajada, Coordination Chemistry Reviews, 2016, 307, 342. (c) J. Cases Díaz, M. Giménez-Marqués, unpublished work.

Biography:

Mónica Giménez Marqués is a Ramón y Cajal Fellow (2019) at the Institute of Molecular Science (ICMol) of the University of Valencia (UV). Her research is devoted to the preparation of hybrid nanoparticles including Metal-Organic Frameworks (MOFs).

She holds a PhD in Nanoscience and Nanotechnology from the UV (Nov. 2013) where she focused in molecular magnetism. During her postdoctoral research in France (2014-2018) she moved her interests towards different uses of MOFs, exploring biomedical uses and catalysis as a Marie-Sklodovska Curie Fellow.

In 2018 she came back to Spain as a Juan de la Cierva Incorporation Fellow, and since then has consolidated her independent career with the support of the Spanish MICINN and different programs such as the Junior Leader La Caixa Incoming and Subvenciones a la Excelencia de Juniors investigadores (Generalitat Valenciana).

She has been distinguished with different scientific awards including the VI Young Talent Award CV (2018), XIV Algemesí Scientific and Technical Award (2019) and was selected to attend the 67^th Lindau Nobel Laureate Meeting.

Title: Reassessing alkyne coupling reactions while studying the electronic properties of diverse pyrene linkages at surfaces

Abstract:

Synthetic organic materials have gained an irrevocable presence in our daily lives. The variety of their applications is continuously growing, including highly refined functionalities. In the frame of their synthesis, on-surface chemistry under vacuum is rapidly attracting increasing attention. The most common functional groups utilized are halogens and alkynes, and the combination of both in the same molecule allows for the possibility of many different reactions. Here, we use a pyrene-based precursor with both functionalities to examine the preferential reaction pathway when it is heated on a Au(111) surface. Using high-resolution bond-resolving scanning tunneling microscopy, we identify multiple stable intermediates along the prevailing reaction pathway that initiates with a clearly dominant Glaser-coupling, together with a multitude of other side products. Importantly, control experiments with reactants lacking the halogen functionalization reveal the Glaser-coupling to be absent and instead show the prevalence of non-dehydrogenative head-to-head alkyne coupling. We perform scanning tunneling spectroscopy on a rich variety of the product structures obtained in these experiments, providing key insights into the strong dependence of their HOMO-LUMO gaps on the nature of the intramolecular coupling. A clear trend is found of a decreasing gap that is correlated with the conversion of triple bonds to double bonds via hydrogenation and to higher levels of cyclization, particularly with non-benzenoid product structures. We rationalize each of the studied cases.

 Biography:

Dimas G. de Oteyza graduated in physics from the Universidad Complutense de Madrid in 2001. In 2003 he embarked the PhD Program of the Universidad Autónoma de Madrid, although performing his investigations at the Max-Planck Institute for Metals Research (Stuttgart, Germany). During this time he performed his first research stay at the National Institute for Materials Science (Tsukuba, Japan), which he has repeated on multiple occasions henceforth. After graduating in 2007 he moved as a postdoc to the Donostia International Physics Center, working at the Nanophysics Laboratory lead by Prof. Enrique Ortega. In 2010 Dimas joined the Molecular Foundry of the Lawrence Berkeley National Laboratory in California as a postdoc, from where he moved to Michael Crommie’s group at the University of California at Berkeley as a Marie Curie Postdoc Fellow in 2011. He finally moved back to San Sebastian in 2013, where he is currently employed as an Ikerbasque Research Professor studying molecular systems on inorganic surfaces. In 2017 and forthcoming years he has been performing periodic research stays in Prof. Kern’s group at the Max-Planck Institute for Solid State Research (Stuttgart, Germany). He received the Fonda-Fasella Award from the Elettra synchrotron in 2013 and the Friedrich Wilhelm Bessel Research Award from the Alexander von Humboldt Foundation in 2017.