Project period: 2022-2026
Funding: NCN Opus 22, UMO-2021/43/B/ST4/00122
PI: dr hab. Bartosz Trzaskowski
Summary: The main goal of this research project is a systematic study of new bis-N-heterocyclic carbene (bis-NHC) and other bis-carbene ruthenium complexes as olefin metathesis catalysts for reactions, which are difficult to perform using standard ruthenium metathesis catalysts. The main part of this project consists of the design and computational modelling of ruthenium complexes incorporating not one carbene (as in standard metathesis catalysts), but two carbenes and their potential use in demanding olefin metathesis reactions such as ring opening metathesis polymerization (ROMP) and selective ring closing metathesis (RCM) to yield tetrasubstituted double bonds. In this work, we will use a quantum chemistry approach to a) obtain a better understanding of the structural and electronic features of ruthenium complexes and carbenes that allow the formation of such bis-NHC systems in contrast to systems containing a single NHC moiety, b) explore the vast chemical space of potential bis-NHC ruthenium complexes with respect to their stability, c) study the entire catalytic pathways of selected olefin metathesis reactions catalyzed by bis-carbene ruthenium complexes to test their applicability to perform such reactions, and d) synthesize selected bis-NHC and bis-carbene complexes to validate out computational results. The results of this project will allow for a thorough characterization of a series of novel metal complexes, potential catalysts, able to perform olefin metathesis (one of the most important chemical reactions of the 21st century) and allow us to develop a general methodology, which will be used in the future to design more advanced catalysts.
Selected publications
coming soon ...
Project period: 2022-2025
Funding: NCN Opus 20, UMO-2020/39/I/ST4/01446
PI: dr hab. Silvio Osella
Summary: The overarching goal of LOW-LIGHT is to rationally design stable and highly efficient hybrid nanomaterials for optoelectronic applications, which include light harvesting/conversion and light emission, to be implemented in proof-of-concept devices. The rational hybridization of all carbon-based nano-objects (the Nano Building Blocks, NBBs) and their formulation into stable colloidal dispersions ready for thin films processing are essential activities that constitute the core of LOW-LIGHT ambitious objectives. Key to this development is the control of the interactions and self-assembly properties of the NBBs at the nanoscale, in order to optimize the structure-property-function relationships in the integrated nano-systems, with the aim of mimicking the perfection of natural structures for light conversion. The nano-hybrids approach proposed by LOW-LIGHT thus represent a merging point between the highly efficient commercial solutions mostly based on inorganics and the chameleonic purely organic electronics.
Selected publications
coming soon ...
Project period: 2019-2023
Funding: NCN Opus 15, UMO-2018/29/B/ST4/00805
PI: dr hab. Bartosz Trzaskowski
Summary: The main goal of this research project is a systematic study of homogenous catalysts based on mechanically interlocked molecules directed toward better understanding of the fundamental aspects of their action. The main part of this project consists of the design and computational modelling of new mechanically interlocked catalysts incorporating carbenes in their structure. We will focus on the use of such systems in both organocatalysis as well as transition metal catalysis, with particular emphasis on designing candidates for efficient stereoselective metathesis catalysts. Controlling stereoselectivity in metathesis reactions, and cross-metathesis in particular, has long been a goal of research, as there is a pressing need to develop reliable routes to stereopure internal olefin products. In this work we will use a combined molecular dynamics / reactive force-field / quantum chemistry approach to explore both the static and dynamic properties of the newly designed systems. This task will be carried out in an interdisciplinary team consisting of scientists - experts in rational design and modeling of transition metal complexes, organometallic chemistry and physics. The results of this project will allow for an accurate characterization of a series of new mechanically interlocked molecules, potential catalysts and allow to develop a general methodology, which will be used in the future to design new, better catalysts.
Selected publications
J.P. Martinez, B. Trzaskowski, "Olefin metathesis catalyzed by a Hoveyda-Grubbs-like complex chelated to bis(2-mercaptoimidazolyl) methane: a predictive DFT study", J. Phys. Chem. A, 126, 720-732 (2022). doi: 10.1021/acs.jpca.1c09336
J.P. Martinez, B. Trzaskowski, "On the Stereoselectivity of the Cross Metathesis of Olefins Catalyzed by a Second-Generation Catalyst", Cat. Commun., 172, 106552 (2022). doi: 10.1016/j.catcom.2022.106552
Project period: 2020-2023
Funding: NCN Sonata 15, UMO-2019/35/D/ST4/01861
PI: dr Magdalena Jawiczuk
The main goal of the proposed research project is a systematic study of novel ruthenium-based catalysts able to catalyze hetero-functional cross metathesis reaction between diazo compounds and alkene to introduce a relevant new tool into imine synthesis. Molecules of this type, containing carbon-nitrogen double bond, belong to important class of chemical compounds. The imine motif can be often found in pharmacologically relevant compounds, for e.g. drugs for Alzheimer’s disease, drugs against osteoporosis. The reversible nature of the imine bond makes it an excellent reactant for construction of imine-based molecular motors, which have been awarded the Nobel Prize. The use of readily available diazenes as substrates for such transformation seems an obvious choice to further expand the scope of cross metathesis, because - as commonly used dyes - they are available in functionalized form and in large quantities. The working hypothesis of the current proposal is based on the assumption that cross metathesis between functionally different unsaturated compounds can be realized, and a properly designed metathesis catalyst will allow to carry out this process catalytically. Our mechanistic study will expand the understanding of structure-activity relationships for the nonstoichiometric azo cross-metathesis transformations.
Selected publications
M. Jawiczuk, N. Kuźmierkiewicz, A.M. Nowacka, M. Moreń, B. Trzaskowski, "A mechanistic, computational study of alkene-diazene heterofunctional cross metathesis catalyzed by ruthenium complexes", Organometallics, 42, 146-156 (2023). doi: 10.1021/acs.organomet.2c00516
Project period: 2019-2022
Funding: NCN Sonata 14, UMO-2018/31/D/ST4/01475s
PI: dr Silvio Osella
Summary: The goal of this project is to expand our knowledge of hybrid, complex protein-graphene interfaces by assembling a multidisciplinary team of computational chemists and physicist. The research project focuses on the computational study of a new hybrid protein-graphene interface, as a possible candidates for bio-electronic devices, such as biosensors, bio-organic photovoltaic cells (bio-OPV) and bio-organic transistors (bio-OFET). The proteins under investigation are small light harvesting proteins (SLPH), interacting with a graphene layer as conducting material as well as charge carrier by means of different molecular linkers (SAM). The interaction and stability of the SLHP/SAM/graphene interface are key parameters to investigate the nature of the interface. Through the use of different computational methods, we will investigate on the one hand the conformational stability and the strength of the interactions at the interface, and on the other hand we will use state-of-the-art methods to account for optoelectronic properties and energy and electron transport mechanisms.
Selected publications
M. Izzo, M. Jacquet, S. Osella, M. Kiliszek, E. Harputlu, A. Starkowska, A. Łasica, G. Unlu, T. Uspienski, P. Niewiadomski, D. Bartosik, B. Trzaskowski, K. Ocakoglu, J. Kargul, "Enhancement of Direct Electron Transfer in Graphene Bioelectrodes Containing Novel Cytochrome c553 Variants with Optimized Heme Orientation", Bioelectrochemistry, 140, 107818 (2021). doi: 10.1016/j.bioelechem.2021.107818
Project period: 2019-2022
Funding: NCN Preludium 16, UMO-2018/31/N/ST4/01394
PI: mgr Katarzyna Młodzikowska-Pieńko
Summary: The main goal of this research project is a systematic study the possible degradation pathways of ruthenium metathesis catalysts. Olefin metathesis is widely use organic reaction, that has been an important synthetic tool in forming the double carbon-carbon bonds. Metathesis requires metal catalysts, and the most common are complexes based on ruthenium. These complexes are often classified as Grubb’s catalysts and Hoveyda-Grubbs catalysts (with chelating the ispopropoxystyrene ligand). In this project we will use a quantum chemistry approach to explore the degradation pathways of metathesis catalysts on the atomic scale.
Selected publications
K. Młodzikowska-Pieńko, B. Trzaskowski, "Decomposition of ruthenium metathesis catalysts: unsymmetrical N-heterocyclic carbenes (uNHCs) versus cyclic alkyl amino carbenes (CAACs)", Organometallics, 41, 3627–3635 (2022). doi: 10.1021/acs.organomet.2c00432
Project period: 2018-2020
Funding: NCN Beethoven 2, UMO-2016/23/G/ST5/04297
PI: dr hab. Bartosz Trzaskowski
Summary: The main goal of this research project is a systematic study of selected, non-standard carbenes and their potential use in homogenous chemical catalysts directed toward better understanding of the fundamental aspects of their action. The main part of this project consists of the design, modelling, synthesis and analysis of new anionic N-heterocyclic carbene derivatives and borylanions, which can be used as transition metal complexing agents to produce new catalysts. We will focus on ruthenium-based complexes as candidates for efficient metathesis reaction but also explore synthetic routes towards complexes of other transition metals. This task will be carried out in an interdisciplinary, multinational team consisting of scientists, experts in carbene synthesis, experimental ruthenium-catalyst preparation and analysis and rational design and modeling of transition metal complexes. The results of this project will allow for an accurate characterization of a series of new carbenes and complexes and allow to develop a general methodology, which will be used in the future to design new, better catalysts.
Selected publications
P. Martinez, B. Trzaskowski, "Structural and Electronic Properties of Boranes Containing Boron-Chalcogen Multiple Bonds and Stabilized by Amido Imidazoline-2-imine Ligands", Chem. Eur. J., 28, e202103997 (2022). doi: 10.1002/chem.202103997
L. Denker, B. Trzaskowski, R. Frank, "“Give Me Five” - An Amino Im-idazoline-2-imine Ligand Stabilises First Neutral Five-membered Cyclic Triel(I) Carbenoides", Chem. Commun., 57, 2816-2819 (2021). doi: 10.1039/D1CC00010A
H. Dolati, L. Denker, B. Trzaskowski, R. Frank, "Superseding β-Diketiminato Ligands: An Amido Imidazoline-2-Imine Ligand Stabilizes the Exhaustive Series of B=X Boranes (X = O, S, Se, Te)", Angew. Chem. Int. Ed., 60, 4633-4639 (2021). doi: 10.1002/anie.202015553
Project period: 2017-2021
Funding: NCN Sonata Bis 6, UMO-2016/22/E/ST4/00573
PI: dr hab. Bartosz Trzaskowski
Summary: The main part of this project consists of the design and modelling of new anionic, cationic and mesoionic N-heterocyclic carbene derivatives, which can be used as transition metal complexing agents to produce new catalysts. We will focus on ruthenium-based complexes as candidates for efficient metathesis, hydrogenation, transfer hydrogenation and hydrosilylation catalytic reactions. For these complexes we will computationally explore all possible catalytic reactions paths and degradation paths and select the best candidates for efficient catalysts for the synthesis. The second theme of this proposal is the development of new computational methods to accurately describe newly designed complexes not only at the atomic level but also at the nano/mesoscale level. This task will be carried out in an interdisciplinary team consisting of scientists, experts in rational design and modeling of transition metal complexes, organometallic chemistry and physics.
Selected publications
M. Jawiczuk, A. Marczyk, B. Trzaskowski, "Decomposition of ruthenium olefin metathesis catalyst; a review", Catalysts, 10, 887 (2020). doi: 10.3390/catal10080887
M. Jawiczuk, A. Marczyk, K. Młodzikowska-Pieńko, B. Trzaskowski, "Impact of the Carbene Derivative Charge on the Decomposition Rates of Hoveyda-Grubbs-Like Metathesis Catalysts", J. Phys. Chem. A, 124, 6158-6167 (2020). doi: 10.1021/acs.jpca.0c03096
M. Jawiczuk, K. Młodzikowska-Pieńko, B. Trzaskowski, "Impact of the olefin structure on the catalytic cycle and decomposition rates of Hoveyda-Grubbs metathesis catalyst", Phys. Chem. Chem. Phys., 22, 13062-13069 (2020). doi: 10.1039/D0CP01798A
K. Młodzikowska-Pieńko, B. Trzaskowski, "Rate-Limiting Steps in the Intramolecular C-H Activation of Ruthenium N-Heterocyclic Carbene Complexes", J. Phys. Chem. A, 124, 3609-3617 (2020). doi: 10.1021/acs.jpca.0c01354