CV_KU_2016_Feb.docx 27.66 kB
- (2014 - 2016) NewFelPro Outgoing Fellowship Scheme: Clean and solvent-free synthesis of microporous materials by mechanochemical assembly and templating under controlled gas atmospheres (FP-7-Marie Curie People COFUND)
- (2016-2018) Croatian Science Foundation: Mechanochemical reactivity under controlled temperature and atmosphere for clean synthesis of functional materials, ca 160 000 EUR.
Awards and Achievements
2014-2015 NewFelPro Scholarship - Postdoctoral Researcher at McGill University, Montreal
2013 - Award for distinguished scientific contribution from RB Institute
2013-2015 - Awards from Division of Physical Chemistry, RB Institute, for scientific publications.
2009 - "National award for excellence" obtained from Croatian Ministry of Science, Sports and Education.
More than 3000 working hours teaching laboratory and seminal courses in General and Inorganic Chemistry for students in chemistry, biology, geology and physics.
Mentor to 10 graduate students in their obtaining of Master Degree. Studies with five of those students were published in four scientific articles.
Mentor to PhD student - field of organic mechanochemical synthesis.
Mentor to one student project: “Concomitant trimorph of cis-dioxo[(N-3-oxypirid-2-yl)-salicydeneiminato-O,N,O'-methanol] molybdenum(VI)” awarded by “Dean’s Award”.
● Igor Huskić, Jan-Constantin Christopherson, Krunoslav Užarević, Tomislav Friščić, In situ monitoring of vapour-induced assembly of pharmaceutical cocrystals using a benchtop powder X-ray diffractometer, Chem. Commun. (2016), 52, 5120-5123; DOI: 10.1039/C6CC01583B
● Patrick A. Julien, Krunoslav Užarević, Athanassios D Katsenis, Simon A. J. Kimber, Timothy C. Wang, Omar K. Farha, Yuancheng Zhang, Jose Casaban, Luzia Germann, Martin Etter, Robert E. Dinnebier, Stuart L. James, Ivan Halasz, Tomislav Friščić,In situ monitoring and mechanism of the mechanochemical formation of a microporous MOF-74 framework, J. Am. Chem. Soc.(2016), DOI: 10.1021/jacs.5b13038.
● Krunoslav Užarević, Timothy C. Wang, Su-Young Moon, Athena M. Fidelli, Joseph T. Hupp, Omar K. Farha, Tomislav Friščić, Mechanochemical and Solvent-free Assembly of Zirconium-Based Metal-organic Frameworks, Chem. Commun. (2016), 52, 2133-2136.
● K. Užarević, Ivan Halasz, Tomislav Friščić, Real-Time and In Situ Monitoring of Mechanochemical Reactions: A New Playground for All Chemists, J. Phys. Chem. Lett. (2015), 6, 4129–4140.
● A. D. Katsenis, V. Štrukil, C. Mottillo, P. A. Julien K. Užarević, M-H. Pham, T-O. Do, S. A. J. Kimber, P. Lazić, O. Magdyshyuk, R. E. Dinnebier, I. Halasz, T. Friščić, In situ X-ray diffraction monitoring of a mechanochemical reaction reveals a unique topology metal-organic framework, Nature Communications, (2015), 6, doi:10.1038/ncomms7662.
● D. Gracin, V. Štrukil, T. Friščić, I. Halasz, K. Užarević, Laboratory real-time and in situ monitoring of mechanochemical milling reactions using Raman spectroscopy, Angew. Chem. Int. Ed. (2014), 53, 6193-6197 (corresponding author).
● K. Užarević, I. Halasz, I. Đilović, N. Bregović, M. Rubčić, D. Matković-Čalogović and V. Tomišić, Dynamic molecular recognition in the solid state for separating mixtures of isomeric dicarboxylic acids, Angewandte Chemie International Edition (2013) 52, 5504-5508. (corresponding author)
● M. Rubčić, K. Užarević, I. Halasz, N. Bregović, M. Mališ, I. Đilović, Z. Kokan, R. S. Stein, R. E. Dinnebier and V. Tomišić, Desmotropy, Polymorphism, and Solid-State Proton Transfer: Four Solid Forms of an Aromatic o-Hydroxy Schiff Base, Chemistry - A European Journal (2012) 18, 5620–5631; (corresponding author)
● K. Užarević, I. Ðilović, N. Bregović, V. Tomišić, D. Matković-Čalogović, and M. Cindrić, Anion-Templated Supramolecular C3-Assembly for Efficient Inclusion of Charge- Dispersed Anions into Hydrogen-Bonded Networks, Chemistry - A European Journal (2011), 17, 10889-10897. (corresponding author)
● K. Užarević, M. Rubčić, M. Radić, A. Puškarić, and M. Cindrić, Mechanosensitive metal–ligand bonds in the design of new coordination compounds. CrystEngComm (2011), 13, 4314-4323. (corresponding author)
● I. Halasz, M. Rubčić, K. Užarević, I. Ðilović, and E. Meštrović, The cocrystal of 4-oxopimelic acid and 4,4’-bipyridine: polymorphism and solid state transformations, New Journal of Chemistry (2011), 35, 24–27
● K. Užarević, M. Rubčić, I. Ðilović, Z. Kokan, D. Matković-Čalogović, and M. Cindrić, Concomitant Conformational Polymorphism: Mechanochemical Reactivity and Phase Relationships in the (Methanol)cis-dioxo-(N-salicylidene-2-amino-3-hydroxypyridine) molybdenum(VI) Trimorph, Crystal Growth and Design (2009), 9, 5327–5333. (corresponding author)
● K. Užarević, I. Ðilović, D. Matković-Čalogović, D. Šišak, and M. Cindrić, Anion-Directed Self-Assembly of Flexible Ligands into Anion-Specific and Highly Symmetrical Organic Solids, Angewandte Chemie International Edition (2008) 47, 7022–7025.
Membership in professional associations / societies
Croatian Chemical Society
Croatian Crystallographic Association
Canadian Institute of Chemistry
Reviewer for CrystEngComm and Journal of Molecular Structure
Scientific interests and motivation
My general scientific interests are in the solid-state chemistry of supramolecular host-guest complexes and in the field of coordination compounds, with special emphasis on microporous metal-organic frameworks. In my research, I combine and compare solution- and solvent-free approaches for synthesis and manipulation of target compounds. These solid-state approaches include mechanochemistry, thermal methods and gas-solid reactions.
In situ methods for monitoring of mechanochemical and vapour-induced solid-state rections
Development of instrumentation and methodology for the in situ monitoring of mechanochemical reactions is performed in collaboration with Friščić Research Group from McGill University, Montreal. It was motivated by almost complete lack of knowledge about the mechanisms of milling reactions, despite their popularity in the materials chemistry and green synthesis. Our recently developed methods for in situ monitoring by synchrotron X-ray diffraction (Nature Chem, (2013), 5, 66; J. Phys. Chem. Lett. (2015), 6, 4129) and by Raman spectroscopy (Angew. Chem. Int. Ed. (2014), 53, 6193) offered unique insight into mechanochemical milling reactivity. They revealed complex behaviour of mechanochemical solid-state reactions, which often proceed in stepwise manner involving different intermediates and provided means for evaluating the role of additives on milling reactions.
Flexible anion receptors
Major part of my research in the field deals with flexible anion receptors, i.e. molecules that employ specific binding functionalities to recognise and selectively bind target specie. During the recognition process, such receptors can change their conformation to adapt to the specific requirements of the guest, and they rarely display high peak selectivity in solution. However, in such systems selectivity is often achieved by selective crystallisation. In our studies, we have developed highly adaptable[1,2] and at the same time highly selective receptor for environmentally important nitrate and sulfate anions. By crystallisation of receptor-anion complexes to hydrogen-bonded networks, these anions were separated form solutions containing large excess of competing anions.
In our latest study we proved that flexible polyamine receptor is capable to recognise and selectively bind isomeric organic guests from their solid mixtures during the milling process. Regardless of whether the recognition takes place in the solid state via milling or by crystallisation from solution, the resulting supramolecular complexes are the same and the selectivity bias of the receptor towards the guest acids is fully retained. Milling improved yields to quantitative and almost eliminated the use of solvent.
Mechanosensitive metal-ligand bonds in the synthesis of new coordination compounds
In the design of discrete and extended coordination systems, synthesis from preorganized homoleptic or heteroleptic coordination compounds is often utilised. Although each of the types is valuable under specific synthetic requirements, heteroleptic complexes tend to be more advantageous when only a certain amount and type of ligands need to be replaced (ancillary). Such an approach also allows a high level of control over the resulting structure because substitution takes place only at strictly defined coordination sites. We employed various solvent-free approaches (mechanochemistry, thermal methods) to selectively remove specific ligand from the central metal coordination sphere, resulting in coordinatively unsaturated compound. Coordinatively unsaturated complexes, due to their higher reactivity, can be considered as “activated” species and as such are better precursors since there is no competition (discrimination) between the departing and the incoming ligand. In our studies we compare solution and solvent-free synthetic approaches which prove to be superior under specific conditions and their respective advantages and weaknesses are object of examination. While our recent studies included complexes with one mechanosensitive bond, we are concentrated on the study of precursors with two or more mechanosensitive sites and they potential application in the controllable synthesis of higher-ordered coordination networks.
Specific class of ligands used in our laboratory for synthesis of coordination compounds are characterised by strong intramolecular N…H…O hydrogen bond and can occur in the solid state as keto-amino or enol-imino tautomers. Proton transfer in such compounds is usually related with their reactivity, but also with macroscopic properties such as thermochromism and photochromism. Although such compounds and accompanying phenomena have been widely studied, the mechanism of this apparently simple solid-state rearrangement still presents a number of challenges. Main reason for this is that, in contrast to solution, where different tautomers coexist, in the solid state usually only one tautomer appears. Our studies included synthesis of the compounds comprising keto-amino and enol-imino subunits and a unique example of a Schiff base which have crystallised separately as a two polymorphic pairs of keto-amino and enol-imino tautomers, i.e. desmotrops. The relative stabilities and interconversions of the four phases were assessed via various solution and solid-state methods and evaluated against the results of a computational study. Our findings emphasize the importance of intermolecular forces in stabilization of the less stable keto tautomer in the solid state.
 K. Užarević, I. Ðilović, D. Matković-Čalogović, D. Šišak, and M. Cindrić, Angew. Chem. Int. Ed. (2008) 47, 7022–7025.
 K. Užarević, I. Ðilović, N. Bregović, V. Tomišić, D. Matković-Čalogović, and M. Cindrić, Chem. Eur. J. (2011), 17, 10889-10897. (corresponding author)
 K. Užarević, I. Halasz, I. Đilović, N. Bregović, M. Rubčić, D. Matković-Čalogović and V. Tomišić, Angew. Chem. Int. Ed. (2013) prihvaćen za objavljivanje, doi: 10.1002/anie.201301032. (corresponding author)
 K. Užarević, M. Rubčić, I. Ðilović, Z. Kokan, D. Matković-Čalogović, and M. Cindrić, Cryst. Growth Des. (2009), 9,5327–5333. (corresponding author).
 K. Užarević, M. Rubčić, M. Radić, A. Puškarić, and M. Cindrić, CrystEngComm (2011), 13, 4314-4323. (corresponding author)
 K. Užarević, M. Rubčić, V. Stilinović, B. Kaitner and M. Cindrić, J. Mol. Struct. 984 (2010), 232-239. (corresponding author)
 M. Rubčić, K. Užarević, I. Halasz, N. Bregović, M. Mališ, I. Đilović, Z. Kokan, R. S. Stein, R. E. Dinnebier and V. Tomišić, Chem. Eur. J. (2012) 18, 5620–5631. (corresponding author)