Izbornik
 

PROJEKT / PROJECT: MOLART

IP-06-2016-4221

 

Trajanje / Duration: 1.3. 2017 - 28. 2. 2021.

 

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

 

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
  • Tekstilno-tehnološki fakultet, Sveučilište u Zagrebu / Faculty of Textile Technology, University of Zagreb 
  • INA-industrija nafte d.d.
  • Dectris Ltd., Baden


NAZIV PROJEKTA / PROJECT TITLE

Metalosupramolekulske strukture i anorgansko-organski polioksometalatni hibridi

Metallosupramolecular architectures and inorganic-organic polyoxometalate based hybrides

 

SAŽETAK 

Glavna ideja projekta temelji se na principima koordinacijske kemije u dizajnu i sintezi novih MoVI metalosupramolekulskih struktura i organsko-anorganskih hibridnih polioksometalatnih materijala. Sinteza novih spojeva bazirat će se na “bottom-up” pristupu, odnosno njihovoj pripravi iz građevnih blokova nastalih in situ kako u otopini tako i u čvrstom stanju. To će omogućiti ispitivanje procesa samoudruživanja i kristalnog rasta navedenih sustava. Poveznica svih segmenata istraživanja je i u pronalaženju uvjeta neophodnih u kontroli sastava, strukture i svojstava ciljnih spojeva. Očekuje se da će ovo istraživanje dati uvid u mehanizme ispitivanih reakcija i omogućiti tumačenje utjecaja različitih inter- i intramolekulskih interakcija na svojstva višedimenzionalnih sustava ili njihovih građevnih blokova. Metode koje će se koristiti u sintezi organskih, metalosupramolekulskih i anorgansko-organskih polioksometalatnih hibrida bit će modificirane metode otopinske kemije, ali će se koristiti i metodologije zelene kemije. Istraživanja termički induciranih reakcija u čvrstom stanju predstavljaju dodatni izazov ovoga projekta.

Predloženi projekt uključivat će organsku, koordinacijsku, analitičku teorijsku, te biokemiju i medicinsku kemiju. Sastoji se od sljedećih dijelova: (i) dizajna i sinteze multifunkcionalnih hidrazonskih N,O-donorskih liganada i ispitivanja njihovih svojstava; (ii) sinteze novih MoVI metalosupramolekulskih sustava; (iii) sinteze novih hibridnih organsko-anorganskih polioksometalatnih spojeva; (iv) karakterizacije svih priređenih spojeva; (v) kvantno-kemijskih proračuna i teorijskih tumačenja eksperimentalnih rezultata s ciljem boljeg razumijevanja i poboljšanja ispitivanih procesa; (vi) ispitivanja kemijskih i fizikalnih svojstava priređenih spojeva; (vii) ispitivanja bioloških svojstava odabranih spojeva.

 

ABSTRACT 

The main idea of the project is to apply principles of coordination chemistry to design and synthesise new MoVI metallosupramolecular architectures and POM-based organic-inorganic hybrid materials. Such systems will be developed via a bottom-up approach combining suitable building blocks generated in situ in solution as well as in the solid state. The complexity in their construction is an invaluable opportunity to study the self-assembly and crystal growth processes. Links between all segments of this research are in finding suitable conditions that are necessary to control the composition and/or structural features of target architectures. It is expected that our investigation will give insight into particular reaction mechanisms and provide explanation for the influence of different inter- and intramolecular interactions on properties of high-dimensional compounds or their building blocks. Methods used in the synthesis of organic, metallosupramolecular and inorganic-organic hybrids will be modified and performed in accordance to conventional, but also green, chemical methodologies. Investigations of thermally induced reactions in the solid state are additional challenging part of the project.

The proposed project will combine organic, coordination, analytical, theoretical, biochemical and medicinal chemistry. The proposed project consists of the following parts: (i) design and synthesis of multifunctional hydrazone N,O-donor ligands and study of their properties; (ii) synthesis of novel MoVI metallosupramolecular architectures; (iii) preparation of novel hybrid organic-inorganic compounds based on polyoxomolybdates; (iv) characterisation of all prepared compounds; (v) quantum chemical calculations and theoretical support to the experimental research which will be used to understand and guide the improved efficiency of the studied processes; (vi) investigation of chemical and physical properties of prepared compounds; (vii) investigation of biological properties of selected compounds.

 

PROJEKTNI TIM / PROJECT TEAM

Prirodoslovno-matematički fakultet / Faculty of Science: prof. dr. sc. Marina Cindrić, prof. dr. sc. Tomica Hrenar, Dino Kuzman, mag. chem., Mirna Mandarić, mag. chem., dr. sc. Jana Pisk, izv. prof. dr. sc. Ines Primožič, prof. dr. sc. Biserka Prugovečki, izv. prof. dr. sc. Mirta Rubčićdoc. dr. sc. Vladimir Stilinović (do 15. 12. 2018.), Edi Topić, mag. chem.,  prof. dr. sc. Višnja Vrdoljak

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

Tekstilno-tehnološki fakultet / Faculty of Textile Technology: prof. dr. sc. Gordana Pavlović (do 1. 3. 2019)

INA-industrija nafte d.d.: dr. sc. Jelena Parlov Vuković

Dectris Ltd: dr. sc. Dubravka Šišak Jung

 

PUBLIKACIJE / PUBLICATIONS

I RAZDOBLJE

  1. J. Pisk, T. Hrenar, M. Rubčić, G. Pavlović, V. Stilinović, V. Damjanović, J. Lovrić, M. Cindrić, V. Vrdoljak, Comparative studies on conventional and solvent free
    synthesis toward hydrazones: application of PXRD and chemometric data analysis in mechanochemical reaction monitoring
    , CrystEngComm, 20 (2018) 1804-1817.
  2. M. Cindrić, V. Stilinović, M. Rubčić, G. Medak, D. Šišak Jung, V. Vrdoljak, Supramolecular assembly of oxalatomolybdates controlled by the hydrogen bonding potential of Co(III)-ammine cations, CrystEngComm, 20 (2018) 1889-1898.

    II RAZDOBLJE

  3. V. Vrdoljak,  B. Prugovečki, I. Primožič, T. Hrenar, D. Cvijanović, J. Parlov Vuković, R. Odžak, M. Skočibušić, S. Prugovečki, J. Lovrić, D. Matković-Čalogović and M. Cindrić, An integrated approach (synthetic, structural and biological) to the study of aroylhydrazone salts, New J. Chem., 42 (2018) 11697-11707.
  4. M. Rubčić, J. Pisk, K. Pičuljan, V. Damjanović, J. Lovrić, V. Vrdoljak, Symmetrical disubstituted carbohydrazides: from solid-state structures to cytotoxic and antibacterial activity, J. Mol. Struct., 1178 (2019) 222-228. 
  5. D. Cvijanović, J. Pisk, G. Pavlović, D. Šišak-Jung, D. Matković-Čalogović, M. Cindrić, D. Agustin, V. Vrdoljak, Discrete mononuclear and dinuclear compounds containing a MoO22+ core and 4-aminobenzhydrazone ligands: synthesis, structure and organic-solvent-free epoxidation activityNew J. Chem., 43 (2019) 1791-1802
  6. M. Cindrić, V. Stilinović, I. Primožić, T. Hrenar, J. Pisk, V. Damjanović, V. Vrdoljak, D. Kuzman, Mechanochemical synthesis of (poly)oxalatomolybdates: In situ reaction monitoring by PXRD, Inorg. Chim. Acta., 488 (2019) 80-85.

    III RAZDOBLJE

  7.  J. Pisk, M. Rubčić, D. Kuzman, M. Cindrić, D. Agustin, V. Vrdoljak, Molybdenum(VI) complexes of hemilabile aroylhydrazone ligands as efficient catalysts for greener cyclooctene epoxidation: an experimental and theoretical approach, New J. Chem., 43 (2019) 5531-5542.
  8.  V. Vrdoljak,  M. Mandarić, T. Hrenar, I. Đilović, J.m Pisk, G. Pavlović, M. Cindrić D. Agustin, Geometrically constrained molybdenum(VI) metallosupramolecular architectures: conventional Synthesis versus vapor and thermally induced solid-state structural transformations, Cryst. Growth. Des., 19 (2019) 3000-3011. 
  9. V. Damjanović, J. Pisk, D. Kuzman, D. Agustin, V. Vrdoljak, V. Stilinović, M. Cindrić, The synthesis, structure and catalytic properties of the [Mo7O24(μ-Mo8O26)Mo7O24]16− anion formed via two intermediate heptamolybdates [Co(en)3]2[NaMo7O24]Cl·nH2O and (H3O)[Co(en)3]2[Mo7O24]Cl·9H2O, Dalton Trans., 48 (2019) 9974-9983.
     
  10. V. Damjanović, D. Kuzman, V. Vrdoljak, S. Muratović, D. Žilić, V. Stilinović, M. Cindrić, Hydrothermal Reactions of [CoIII(C2O4)(NH3)4]+ and Polyoxomolybdates: Depolymerization of Polyoxomolybdates and in Situ Reduction of Cobalt, Cryst. Growth Des., 19 (2019) 6763–6773.
  11. M. Mandarić, B. Prugovečki, D. Cvijanović, J. Parlov Vuković, J. Lovrić, M. Skočibušić, R. Odžak, M. Cindrić, V. Vrdoljak, Vapour- and solvent-mediated crystalline transformations in Mo(VI) hydrazone complexes controlled by noncovalent interactions, CrystEngComm, 21 (2019) 6281–6292.

 

POZVANO PREDAVANJE

  1. M. Cindrić, Supramolekulski sustavi funkcionaliziranih polioksomolibdata – od sinteze do svojstava,  II simpozij suprmolekulske kemije, 12. 12. 2018., Zagreb, Hrvatska.
    https://supramolchem2018.irb.hr/Simpozij
  2. V. Vrdoljak, Metallosupramolecular Assemblies: the Synergy Between NMR Spectroscopy and Crystallography,  Adriatic NMR Conference, 6-9.06.2019., Mali Ston, Hrvatska.

 

 

KONFERENCIJE / CONFERENCES

I RAZDOBLJE

  1. M. Cindrić, V. Stilinović, M. Rubčić, V. Vrdoljak, Supramolecular complexes based on molybdates and different Co(III)-ammine units via electrostatic and H-bonding interactions, 4th EuCheMS Inorganic Chemistry conference, 2.-5. 7. 2017., Copenhagen, Danska.
  2. M. Rubčić, J. Pisk, M. Cindrić, V. Vrdoljak, Symmetrical and asymmetrical carohydrazides: A solid-state and solution study, Adriatic NMR, 16.-18. 6. 2017., Mali Ston, Hrvatska.
  3. J. Pisk, M. Rubčić, D. Cvijanović, V. Damjanović, J. Lovrić, M. Cindrić, V. Vrdoljak, Biological testings of mechanochemicaly obtained aroyl hydrazones as perspective ligands for metal complexes, 14th International symposium on applied bioinorganic chemistry-ISABC14, 7.-10. 6. 2017, Toulouse, Francuska.

    II RAZDOBLJE
  4. D. Cvijanović, J. Pisk, G. Pavlović, D. Šišak-Jung, M. Cindrić, V. Vrdoljak, Dinuclear Mo(VI) complexes with 4-aminobenoylhydrazone derivatives: a slid-state amd solution study, Adriatic NMR, 15.-17. 6. 2018., Mali Ston, Hrvatska.
  5. V. Vrdoljak, M. Mandarić, D. Kuzman, M. Rubčić,  G. Pavlović, J. Pisk, M. Cindrić, Metallosupramolecular architectures derived from aroylhydrazone ligands, European Chemistry Conference 2018, ECC-2018, 4.-6. 7. 2018, Rome, Italy.
  6. D. Cvijanović, J. Pisk, G. Pavlović, D. Šišak-Jung, M. Cindrić, D. Agustin, and V. Vrdoljak, The mononuclear MoO22+complexes with stereochemically rigid 4-aminobenzhydrazide based ligands, 31st European Crystallographic Meeting, ECM31, 22.-27. 8. 2018, Oviedo, Spain.
  7. A. Eberhardt, V. Stilinović, V. Vrdoljak, M. Cindrić,  Sinteza i karakterizacija kompleksnih soli, [CoC2O4(NH3)4]2[Co(C2O4)2(H2O), [(C2O4)2Co(μ-OH)2Co(NH3)4]·3H2O, 3Na[CoC2O4(NH3)4][Mo2O4(µ-O)2(C2O4)2] i [CoC2O4(NH3)4]4[Mo3O6(μ-O)2(C2O4)3(H2O)2]·nH2O,
    5. Simpozij studenata kemičara, 27.10. 2018., Zagreb, Hrvatska.
  8. V. Damjanović, J. Pisk, V. Vrdoljak, V. Stilinović, M. Cindrić, Synthetic route influence on the formation of supramolecular Co(III)-Mo(VI) double-complex salts, IUPAC Postgraduate Summer School on Green Chemistry, 7.-13. 7. 2018., Venice, Italy

    III RAZDOBLJE
  9. D. Kuzman,V. Vrdoljak, V. Stilinović, M. Cindrić, Molekulska i kristalna struktura polioksomolibdata građenih od [Mo7O24]6- i [CoMo6(OH)6O18]6- aniona, 26. hrvatski skup kemičara i kemijskih inženjera, 9.-12. 4. 2019, Šibenik, Hrvatska.
  10. E. Topić, M.Rubčić, J. Pisk, V. Vrdoljak, Structural insights into complexes and polyoxomolybdate salts derived from asymmetric carbohydrazones, 6. hrvatski skup kemičara i kemijskih inženjera, 9.-12. 4. 2019, Šibenik, Hrvatska.

  11. D. Cvijanović, M. Mandarić, B. Prugovečki, J. Lovrić, Jasna, M. Cindrić,  V. Vrdoljak, 

    Synthesis, characterization and cytotoxicity of dioxomolybdenum(VI) complexes with 4- methoxysalicylaldehyde isonicotinoyl hydrazone, 6. hrvatski skup kemičara i kemijskih inženjera, 9.-12. 4. 2019, Šibenik, Hrvatska.

  12. M. Mandarić, V. Vrdoljak, T. Hrenar, I. Đilović, M. Cindrić, Vapor and thermally induced solid-state structural transformations, 17th International Conference on Chemistry and the Environment, 16-20.06.2019., Thessaloniki, Grčka.

  13. M. Cindrić, V. Stilinović, V. Damjanović, D. Kuzman, S. Muratović, D. Žilić, V. Vrdoljak, From [Mo7O24]2- to Anderson-type anion [CoII(OH)6Mo6O18]4− in presence of [Co(ox)(NH3)4](NO3) and under hydrothermal conditions, 2nd Euro Chemistry Conference, 17-19.06.2019., Valencia, Španjolska.
  14. M. Mandarić, V. Vrdoljak, Vapor and thermally induced solid-state structural transformations, Solid-State Science & Research Meeting, 27-29.06.2019., Zagreb, Hrvatska.
  15. E. Topić, V. Stilinović, On the molar volume of multicomponent crystals, Solid-State Science & Research Meeting, 27-29.06.2019., Zagreb, Hrvatska.

  16. M. Rubčić, E. Topić, J. Pisk, V. Vrdoljak, Hybrid polyoxomolybdate systems based on rationally designed asymmetric carbohydrazones, 32nd European Crystallographic Meeting, 18-23.08.2019., Beč, Austrija.
  17.  J. Pisk, D. Cvijanović, D. Kuzman, M. Rubčić, D. Agustin, V. Vrdoljak, Greener cyclooctene epoxidation with molybdenum complexes derived from aminobenzohydrazone ligands, Advanced Energy Materials Conference, 11-13.09.2019., Guildford, Engleska. 

LJETNE ŠKOLE

  1. V. Damjanović, S, IUPAC Postgraduate Summer School on Green Chemistry, 7.-13. 7. 2018., Venice, Italy.
  2. M. Mandarić, 17th BCA/CCG Intensive Teaching School in X-Ray Structure Analysis, 6.-14.04. 2019., Durham, Ujedinjeno Kraljevstvo
  3. D. Kuzman, 4th International Summer School of Crystallography, 2.-8.06. 2019., Hamburg, Njemačka
  4. E. Topić, The Zürich School of Crystallography 2019: Bring Your Own Crystals, 16.-27.06. 2019., Zürich, Švicarska

DIPLOMSKI RADOVI/ DIPLOMA THESIS

  1. Kuzman, Dino
    Mononuklearni i dinuklearni kompleksi molibdena(vi) s derivatima 2-benzhidrazida 2017., diplomski rad, Prirodoslovno-matematički fakultet, Zagreb, (mentor: V. Vrdoljak)
  2. Mandarić, Mirna
    Strukturna raznolikost kompleksnih spojeva molibdena(VI) s hidrazonskim ligandima
    2018, diplomski rad, Prirodoslovno-matematički fakultet, Zagreb (mentor: V. Vrdoljak)
  3. Zrnc, Katrina 
    Strukturne transformacije mononuklearnih kompleksa molibdena(VI) s derivatima 4-aminobenzhidrazida, diplomski rad, Prirodoslovno-matematički fakultet, Zagreb (mentor: V. Vrdoljak)
  4. Medak, Glorija
    Reakcije nastajanja oksalatomolibdata s Co(III) etilendiaminskim kationima, 2018, diplomski rad, Prirodoslovno-matematički fakultet, Zagreb (mentor: M. Cindrić)

 

 

 

 


Tražilica
 

 

 

Sva prava pridržana. Kemijski odsjek Prirodoslovno-matematičkog fakulteta
Sveučilište u Zagrebu