During my undergraduate years, I’ve been working on ligands capable of coordinating specific metals. This included a little bit of synthetic work, analysis of the structure (through NMR and XRD) and analysis of thermodynamic properties (using potentiometric, spectrophotometric and NMR titrations). Interest in coordination chemistry led me to inorganic chemistry studies and I acquired detailed knowledge (and a degree as a byproduct) about organometallic compounds, coordination compounds and means to study such species.
Interest in theoretical chemistry struck me during NMR course, where I also met my Ph.D. supervisor. I had two main topics at that time – experimental synthesis of ligands designed for metals such as aluminum and gallium and theoretical prediction of heavy element bonding inside the fullerene cages. After finishing the experimental work, I left practical chemistry and became full-time theoretician.
Currently, I’m trying to connect best of both worlds and use my knowledge of coordination chemistry together with my ability to predict structures and properties computationally.
Heavy element bonding
Some of the heavy elements such as actinides are quite inaccessible to experimental studies due to their instability. Nevertheless, since we’ve seen bizarrely (from the point of view of your usual everyday carbon-based chemistry) bonding transition metals, such as two chromium atoms connected with quintuple bonds, there may be even more bizarre bonding between two actinides. And there is! In my research related to this, I’ve studied early actinides enclosed in the fullerene cage. The cage is kind of a nanolaboratory to study these heavy fellas in and I’m not waving hands here – two uranium atoms and also two thorium atoms forming bond between each other have been experimentally really enclosed in fullerenes. My take on prediction of properties of such systems on DFT level can be seen here.
But (there is always a but, isn’t it) while experiments can give us structure of such species and also some properties, bonding remains mainly in the domain of theoretical chemists. And since we’re talking about really heavy elements with many nucleons and electrons, theory has its issues and limitations (such as relativistic effects or inaccessibility of ab-initio based methods). My main topic as of now is to not only give us an idea of how strong the bonding between enclosed actinides really is but also what methods are appropriate to evaluate that. Stay tuned!
Properties of coordination compounds
As I have stated above, I didn’t really leave the field of coordination chemistry. Merging the hands-on experience with capability of calculating interesting things proved to be useful in either explaining some properties of complex compounds or predicting their geometry and properties. Cooperation with my former group yielded an article about simple, yet complex, um, complex. Cooperation with another group interested in coordination chemistry led to a study of macrocycle-based ligands designed to host lanthanides. Besides these projects, I also use the simplest Werner-like complexes to create useful model for coordination chemistry lectures.
Fullerene-based molecular electronics
Enclosing things into the fullerene cages is fun, so why not move them around with electric field, right? Yeah. We did that too, theoretically. While endohedral fullerenes are not accessible in great amounts and their use in electronics is thus far-fetched, in principle it works. Moreover, systems studied in our group seem to have very specific properties. Imagine a diode and a switch in a single molecule. Boom. You got memristor, mentioned in the article above. And also the other one, but I don’t want to talk about that until it’s published.
Abovementioned systems led us to general study of what diatomic molecule is the best to enclose from both the experimental view and the functionality of the system as an electronic component. Besides that, experimental evidence shows that almost no transition metals can be enclosed in the cages using the state of art methods such as arc discharge and laser ablation. I’m looking into that too.
List of publications
2019 - Poster - Theoretical inorganic chemistry winter school, Helsinki, Finland
2019 - Poster - Nanocon, Brno, Czech Republic
2019 - Poster - Transition metals and spectroscopy summer school, Gelsenkirchen, Germany
2019 - Poster - CECAM 50, Lausanne, Switzerland
2019 - Lecture - MMQC, Mariapfarr, Austria
2018 - Poster - Modern wavefunction methods summer school, Gelsenkirchen, Germany
2018 - Poster - MMQC, Mariapfarr, Austria
2021 - 2022 - Fulbright-Masaryk scholarship - Research of thorium complexes, LANL, USA
2019 - 2020 - Grant Agency of Charles University student grant - Research of endohedral fullerenes, CU, Czech Republic