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Chemistry of novel materials

Exploring the Future of Materials Science: Metal-Organic Frameworks (MOFs) 

Michał Chmielewski, PhD DSc, Assoc. Prof. and the team

One of the most exciting frontiers in 21st-century materials science is the development of Metal-Organic Frameworks (MOFs). These advanced materials consist of metal ions or clusters linked by rigid organic molecules, forming highly porous, three-dimensional structures. What makes MOFs truly remarkable is their regular, tunable porosity, which can be precisely engineered for a wide range of applications, including gas storage and separation, catalysis, drug delivery, sensing, and even harvesting water from air.

At the Faculty of Chemistry, University of Warsaw, MOFs are being explored primarily for use in catalysis, where their porous architecture provides a unique nanoenvironment for chemical reactions. Prof. Chmielewski and his team have developed new methods to immobilise homogenous catalysts within MOFs, improving their stability and reusability in catalytic processes. In collaboration with the team of prof. Grela, they were the first to successfully immobilise catalysts for olefin metathesis—an industrially important reaction—within MOFs.

This work is at the forefront of a rapidly evolving field, contributing to the development of smart, functional materials that will help to shape the future of science and industry.

Selected publications:

  1. Zwoliński, M. J. Chmielewski, “TEMPO-appended Metal–Organic Frameworks as highly active, selective, and reusable catalysts for mild aerobic oxidation of alcohols” ACS Appl. Mater. Interfaces, 2017, 9, 33956, DOI: 10.1021/acsami.7b09914
  2. Chołuj, A. Zieliński, K. Grela, M. J. Chmielewski, “Metathesis@MOF: simple and robust immobilization of olefin metathesis catalysts inside (Al)MIL-101-NH2” ACS Catal., 2016, 6, 6343, DOI: 10.1021/acscatal.6b01048
  3. Chołuj, R. Karczykowski, M. J. Chmielewski, “Simple and robust immobilization of a ruthenium olefin metathesis catalyst inside mofs by acid−base reaction” Organometallics, 2019, 38, 3392, DOI: 10.1021/acs.organomet.9b00281
  4. Dworakowski, A. Chołuj, M. J. Chmielewski, D. Gryko “Vitamin B12 and a metal-organic framework enable the photocatalytic generation of alkyl radicals” Chem. Commun., 2023, 59, 11236; DOI: 10.1039/D3CC02941G
Self-assembled systems 

Prof. Ewa Górecka, PhD DSc; Damian Pociecha, PhD DSc, Assoc. Prof. and the team

Liquid crystals

Liquid crystals, a state of matter discovered over a century ago, exhibit  properties that combine fluidity with directional dependence,  demonstrating the anisotropy characteristic of crystals. Widely utilized  in modern technology, such as computer and TV displays, they are also fascinating subjects for studying complex structures, phase transitions  and unique physical properties. Their beauty captivates generation of researchers; when observed under a polarizing microscope, liquid crystals display  characteristic images decorated with systems of defects.

The liquid crystals exhibit an exceptional variety of structures, ranging from simple ones with only orientational order of molecules to 3D structures with giant repeating units composed of thousands of molecules, e.g. cubic structures built of networks of channels.

Our interest in liquid crystals is mainly related to their complex structures. Specifically, we focus on materials that spontaneously form helices despite being composed of highly symmetric molecules. Remarkably, some of these materials, though fluid, possess strong, long-range dipole order, leading to ferroelectric properties – the electric analog of magnetism. Like solid ferroelectrics, liquid crystalline ones exhibit domain structure to reduce global spontaneous electric polarization. However, they also demonstrate novel mechanisms absent in solids: their molecules spontaneously twist, forming heliconical structures with helix lengths being comparable to the wavelength of visible light.

Selected publications:

  1. Karcz, J. Herman, N. Rychłowicz, P. Kula, E. Górecka, J. Szydlowska, P. W. Majewski, D. Pociecha, “Spontaneous chiral symmetry breaking in polar fluid–heliconical ferroelectric nematic phase” Science, 2024, 384, 1096, DOI: 10.1126/science.adn6812
  2. M. Majewska, E. Forsyth, D. Pociecha, C. Wang, J. M. D. Storey, C. T. Imrie, E. Gorecka, “Controlling spontaneous chirality in achiral materials: liquid crystal oligomers and the heliconical twist-bend nematic phase” Chem. Commun., 2022, 58, 5285, DOI: https://doi.org/10.1039/D1CC07012F
  3. Szydlowska, P. Majewski, M. Čepič, N. Vaupotič, P. Rybak, C. T. Imrie, R. Walker, E. Cruickshank, J. M. D. Storey, P. Damian, E. Gorecka, “Ferroelectric nematic-isotropic liquid critical end point” Phys. Rev. Lett., 2023, 130, 216802, DOI: https://doi.org/10.1103/PhysRevLett.130.216802
  4. Cruickshank, P. Rybak, M. M. Majewska, S. Ramsay, C. Wang,
    C. Zhu, R. Walker, J. M. D. Storey, C. T. Imrie, E. Gorecka,
    D. Pociecha, “To be or not to be polar: the ferroelectric and antiferroelectric
    nematic phases    ” ACS Omega 2023, 8, 36562, DOI: https://pubs.acs.org/doi/10.1021/acsomega.3c05884
Self-assembled systems 

Paweł Majewski, PhD DSc, Assoc. Prof. and the team

Block copolymers

Our research group specializes in functional polymers, self-assembling soft materials, and surface science, with a particular focus on block copolymer and liquid crystal thin films. Among our key achievements is the development of photothermal methods using laser radiation to control supramolecular self-assembly;  for example to produce perfectly ordered block copolymer thin films. We have also shown how block copolymers can be used in synthesizing semiconducting nanowires, which are applied in miniaturized atmospheric pollutants-sensing devices through a straightforward one-pot synthetic process.

Additionally, together with a group of Prof. Lewandowski, we have pioneered a technique utilizing an automatically-driven microscope projection system to inscribe chiral, optically active patterns in liquid crystalline thin films with laser light. These patterns, invisible to the naked eye, hold significant potential for anticounterfeiting applications and the emission of circularly polarized light.

More recently, our work in collaboration with a group of Prof. Graczykowski from Adam Mickiewicz University in Poznan has led to the development of a synthetic pathway for depositing ultra-thin polymeric membranes that are sensitive to light and humidity. These membranes, created through a unique plasma-assisted polymerization technique, exhibit exceptional durability and can function as microscopic actuators controlled by light or as highly sensitive sensors responsive to environmental changes such as humidity and temperature.

Selected publications:

  1. A. Leniart, P. Pula, A. Sitkiewicz, P. W. Majewski, “Macroscopic alignment of block copolymers on silicon substrates by laser annealing” ACS Nano, 2020, 14, 4805, DOI: https://doi.org/10.1021/acsnano.0c00696
  2. Pula, A. A. Leniart, J. Krol, M. T. Gorzkowski, M. C. Suster, P. Wrobel, A. Lewera, P. W. Majewski, “Block copolymer-templated, single-step synthesis of transition metal oxide nanostructures for sensing applications” ACS Appl. Mater. Interfaces, 2023, 15, 57970, DOI: https://doi.org/10.1021/acsami.3c10439
  3. Szustakiewicz, F. Powała, D. Szepke, W. Lewandowski, P. W. Majewski, “Unrestricted chiral patterning by laser writing in liquid crystalline and plasmonic nanocomposite thin films” Advanced Materials, 2023, 36, 2310197, DOI: https://doi.org/10.1002/adma.202310197
  4. Patent pending P.445711
  5. Krysztofik, P. Pula, M. Pochylski, K. Zaleski, J. Gapinski, P. Majewski, B. Graczykowski, „Fast photoactuation and environmental response of humidity-sensitive pDAP-silicon nanocantilevers” Advanced Materials, 2024, 36, 2403114, DOI: https://doi.org/10.1002/adma.202403114
Self-assembled systems 

Wiktor Lewandowski, PhD DSc, Assoc. Prof. and the team

Twisted optical nanomaterials

The NanoOrgMat group focuses on the intersection of organic chemistry and nanomaterials, aiming to develop advanced nanomaterials for applications in photonics, such as next-generation displays, and in medicine, including novel biosensors. We specialize in designing organic compounds that guide the self-assembly process of nanomaterials into hierarchical structures, with properties that can be dynamically tuned under external stimuli, such as temperature or light.

A major highlight of our work is the exploration of material chirality, a property ubiquitous in nature, that allows materials to interact selectively with either left- or right-handed circularly polarized light. We pioneered the creation of thin-film chiral materials using liquid crystals, that form supramolecular chiral structures, such as helices or nanotubes.

The soft character of the LCs facilitates the incorporation of various dopants, such as gold nanoparticles, quantum dots or perovskites with different sizes and morphologies. Guiding their self-assembly into hierarchical, chiral structures leads to enhanced interactions across the UV-Vis-NIR spectrum, which can give the material new functionalities such as chiral sensing, enantioselective catalysis, and advanced photonic applications. As another way to plasmonic chirality we made significant steps in development of morphologically chiral gold nanoparticles, their colloidal stability and adaptability to different environments. These kinds of nanomaterials have great applicative potential in next-generation of biosensors

Selected publications:

  1. Szustakiewicz, N. Kowalska, D. Grzelak, T. Narushima, M. Góra, M. Bagiński, D. Pociecha, H. Okamoto, L. M. Liz-Marzán, W. Lewandowski, “Supramolecular chirality synchronization in thin films of plasmonic nanocomposites” ACS Nano 2020, 14, 12918, DOI: https://doi.org/10.1021/acsnano.0c03964
  2. Bagiński, M. Tupikowska, G. González-Rubio, M. Wójcik, W. Lewandowski, “Shaping liquid crystals with gold nanoparticles: helical assemblies with tunable and hierarchical structures via thin-film cooperative interactions” Adv. Mater. 2020, 32, 1904581, DOI: https://doi.org/10.1002/adma.201904581
  3. Grzelak, M. Tupikowska, D. Vila-Liarte, D. Beutel, M. Bagiński, S. Parzyszek, M. Góra, C. Rockstuhl, L. M. Liz-Marzán, W. Lewandowski, “Liquid crystal templated chiral plasmonic films with dynamic tunability and moldability” Adv. Funct. Mater. 2022, 32, 2111280, DOI: https://doi.org/10.1002/adfm.202111280
  4. Kowalska, F. Bandalewicz, J. Kowalski, S. Gómez-Graña, M. Bagiński, I. Pastoriza-Santos, M. Grzelczak, J. Matraszek, J. Pérez-Juste, W. Lewandowski, “Hydrophobic Gold Nanoparticles with Intrinsic Chirality for the Efficient Fabrication of Chiral Plasmonic Nanocomposites” ACS Appl. Mater. Interfaces 2022, 14, 50013, DOI: https://pubs.acs.org/doi/10.1021/acsami.2c11925