IP-2022-10-7368

Trajanje / Duration: 30. 12. 2023. do 29. 12. 2027.

Financiranje / Funding: HRVATSKA ZAKLADA ZA ZNANOST / CROATIAN SCIENCE FOUNDATION 

VODITELJ PROJEKTA / PRINCIPAL INVESTIGATOR: prof. dr. sc. Višnja Vrdoljak

INSTITUCIJE KOJE SUDJELUJU U PROJEKTU / INSTITUTIONS

• Prirodoslovno-matematički fakultet, Sveučilište u Zagrebu / Faculty of Science, University of Zagreb
• Medicinski Fakultet, Sveučilište u Zagrebu / School of Medicine, University of Zagreb

NAZIV PROJEKTA / PROJECT TITLE:

Supramolekulski i hibridni metalo-organski koordinacijski sustavi – kooperativni učinci i predviđanje aktivnosti/svojstava 

Supramolecular and hybrid metal-organic coordination assemblies – cooperative effects and activity/property prediction

SAŽETAK:

Interes za supramolekulske i hibridne metalo-organske sustave u kojima koordinacija ima ključnu ulogu nije posljedica samo njihovih interesantnih molekulskih struktura već i raznolikosti njihovih svojstava. Stoga ćemo se u ovom projektu baviti dizajnom: (i) metalocikličkih i polimernih sustava vanadija(v) s hidrazonskim i alkokso ligandima, (ii) hibrida temeljenih na Co-makrokationima i polioksovandatima ili V/Mo-heteropolioksometalatima, i (iii) hibrida V/Mo-heteropolioksometalata kovalentno funkcionaliziranih alkokso-hidrazonskim kompleksnim sustavima. Svaki segment istraživanja obuhvaćat će sintetski, fizikalno-kemijski i računalni aspekt.

Cilj ovog projekta ne odnosi se samo na dizajn novih sustava već i na razumijevanje kooperativnih učinaka i mehanizma koji omogućuju njihovo nastajanje te konačno istraživanje njihovih specifičnih svojstava. Detaljna karakterizacija priređenih spojeva bit će ključna za razumijevanje eksperimentalnih i računalnih rezultata istraživanja.

Ovi sustavi poslužit će kao idealni modeli za istraživanje katalitičkih procesa i razumijevanje odnosa strukture i aktivnosti te svojstava spojeva. Istražiivat će se njihova uloga u katalitičkoj oksidaciji derivata benzilnog alkohola korištenjem ekološki prihvatljivih oksidansa. Također, proučavat će se i intramolekulska oksidacija alkokso liganda u supramolekulskim spojevima kako bi se ustanovila uloga vanadijevih intermedijera. Cilj projekta je spoznati kako svojstva spojeva ovise o vrsti liganada, nuklearnosti spoja, ili prirodi heteroatoma.

Opsežni kvantno-kemijski izračuni, strojno učenje, obrada i analize podataka uz eksperimentalno istraživanje omogućit će razumijevanje odnosa strukture i svojstava te mehanizama reakcija. Na temelju eksperimentalnih podataka, važan rezultat istraživanja predstavljat će model predviđanja, koji će se dalje koristiti kao smjernica za dizajniranje novih materijala s poboljšanim i željenim svojstvima.

ABSTRACT:

Interest in coordination-driven supramolecular and hybrid metal-organic assemblies relies not only on their attractive molecular structures but also on their various properties.  In this project, we will therefore address the design of (i) vanadium(v) metallocyclic and polymeric assemblies with hydrazone and alkoxo ligands; (ii) hybrids based on Co-macrocations and polyoxovandates or V/Mo-heteropolyoxometalate anions; and (iii) V/Mo-heteropolyoxometalate hybrids covalently functionalized by alkoxo-hydrazone complex assemblies. Each research segment will have interwoven synthetic, physicochemical, and computational aspects.

The aim of this project is not only the design of novel assemblies but also the understanding of the cooperative effects and mechanisms that enable their formation, and finally, their specific properties. The in-depth characterisation of the prepared compounds will be crucial for understanding the experimental and computational results of the research.

These assemblies will serve as ideal models for testing the catalytic processes and understanding the structure-activity/property relationship. Their role in the catalytic oxidation of benzyl alcohol derivatives using environmentally benign oxidants will be investigated.

The intramolecular oxidation of the alkoxo ligand in the supramolecular compounds will also be studied to clarify the role of the vanadium intermediates. The project aims to determine how the properties and performances of the compounds depend on the type of ligands, compound nuclearity, or the nature of the heteroatom.

Extensive quantum chemical calculations, machine learning, data processing and analyses will support experimental research and provide structure-properties relationships and mechanistic understanding. Based on the experimental data an important result of the investigation will present a prediction model, which will be further used as a guideline for designing new materials with improved and desired properties.

PROJEKTNI TIM / PROJECT TEAM:

Prirodoslovno-matematički fakultet / Faculty of Science: prof. dr. sc. Marina Cindrić, prof. dr. sc. Tomica Hrenar, dr. sc. Dino Kuzman, izv. prof.dr. sc. Jana Pisk, prof. dr. sc. Mirta Rubčić, dr.sc. Edi Topić, prof. dr. sc. Višnja Vrdoljak

Medicinski Fakultet, School of Medicine: doc. dr. sc. Danijela Musija, izv. prof. dr. sc. Vladimir Damjanović, prof. dr. sc. Jasna Lovrić

PUBLIKACIJE / PUBLICATIONS

1. D. Kuzman, V. Damjanović, M. Cindrić, and V. Vrdoljak, Aqueous solution as a playground of {MoO₄}, {Mo₄O₁₂}, {Mo₈O₂₆}, {Mo₈V₅O₄₀} and {V₇Mo₂O₂₇} species in the presence of carboxylic acids and [Co(C₂O₄)(NH₃)₄]⁺ or [Co(en)₃]³⁺ cations, CrystEngComm, 2025, 27, 1128-1138. https://doi.org/10.1039/D4CE01187B.

2. E. Topić, J. Sarjanović, D. Musija, M. Mandarić, T. Hrenar, J. Pisk, and V. Vrdoljak, High-valent oxovanadium metallosupramolecular species as catalysts for the oxidation of benzyl alcohol derivatives, RSC Advances,  2025, 15, 3547 - 3561. https:doi.org/10.1039/d4ra09073j 

3. E. Topić, J. Sarjanović, D. Musija, M. Mandarić, A. Cocut, T. Hrenar, D. Agustin, J. Pisk, and V. Vrdoljak, Influence of ancillary ligands on the formation and functionality of oxovanadium(V) metallosupramolecular assemblies: advanced computational and catalytic analysis, Dalton Transactions, 2025, 54, 5532-5545. https:doi.org/10.1039/D5DT00105F

4.  D. Kuzman, M. Pajić, L. Drempetić, J. Sarjanović, J. Pisk, T. Hrenar, M Cindrić, and V. Vrdoljak, Cobalt Complex-Directed Self-Assembly of a Polyoxometalate-Based Species: Influence of Synthetic Methods on Structure and Properties of Hybrid Assemblies, ACS Omega 2025, 10, 16668–16682, https:doi.org/10.1021/acsomega.5c00186

POZVANO PREDAVANJE / KEYNOTE / INVITED LECTURES

1. Vrdoljak, Višnja; Topić, Edi; Hrenar, Tomica; Mandarić, Mirna; Pisk, Jana - Preparation and post-assembly modification of metallosupramolecular architectures derived from hydrazone-based ligands // 3rd European Congress on Chemistry and Applied Sciences, Amsterdam, Nizozemska, 24.06.2024-25.06.2024.

2. Vrdoljak, Višnja; Exploring the Journey of Vanadium-based Metallosupramolecular Architectures with Hydrazone-Based Ligands,  //Applied Chemistry & Mass Spectrometry and Analytical Techniques, Berlin, Njemačka,  14. 4. 2025 -15. 4. 2025. 

KONFERENCIJE / CONFERENCES

1. Pisk, Jana; Topić, Edi; Agustin, Dominique, Rubčić, Mirta; Vrdoljak, Višnja - Catalytic potential of vanadium coordination compounds in oxidation reactions // 18th Edition of International Conference on Catalysis, Chemical Engineering and Technology Pariz, Francuska, 17.06.2024-19.06.2024.

2. Kuzman, Dino; Drempetić, Lucija; Cindrić, Marina; Vrdoljak, Višnja - The influence of complex cobalt(III) cations and synthetic methods on polyoxovanadate formation // 3rd European Congress on Chemistry and Applied Sciences Amsterdam, Nizozemska, 24.06.2024-25.06.2024.

3. Toplak, Juraj; Kuzman, Dino; Vrdoljak, Višnja - Exploring the fascinating world of copper(II) hydrazone complexes //Applied Chemistry & Mass Spectrometry and Analytical Techniques, Berlin, Njemačka,  14. 4. 2025 -15. 4. 2025. 

4. Kuzman, Dino; Damjanović, Vladimir ; Cindrić, Marina; Vrdoljak, Višnja - Influence of p-block elements on the formation of heteropolyoxometalates with complex cobalt(III) cations //Applied Chemistry & Mass Spectrometry and Analytical Techniques, Berlin, Njemačka,  14. 4. 2025 -15. 4. 2025.

5. Sarjanović, Josipa; Pisk, Jana; Vrdoljak, Višnja -  Smart catalysts for green chemistry: vanadium hydrazone complexes in alcohol oxidation //  2nd International Conference of the Croatian Ceramic Society, Šibenik, Hrvatska, 30.4.2025 -30.5.2025.

6. Toplak, Juraj; Kuzman, Dino; Vrdoljak, Višnja - Reversible single-crystal-to-single-crystal transformations in Cu(II) hydrazonato MOFs // University of Zagreb Faculty of Science PhD Student Symposium, Hrvatska, Zagreb, 28.04.2025.-29.04.2025. 

LJETNE ŠKOLE / SUMMER SCHOOLS

DIPLOMSKI RADOVI/ DIPLOMA THESIS

1. Emanuela Pleić

Sinteza i karakterizacija metalosupramolekulskih spojeva vanadija(V) s hidrazonskim ligandima, 2024., diplomski rad, Prirodoslovno-matematički fakultet, Zagreb, (mentor: V. Vrdoljak)