PROJEKT / PROJECT: FunMaterials

IP-2020-02-4467

 

NAZIV PROJEKTA / PROJECT TITLE: Od aromatskih spojeva s dušikom do novih funkcionalnih organskih materijala / From nitrogen-containing aromatic compounds to new functional organic-based materials

 

Trajanje / Duration: 1.1.2021. – 31.12. 2024.

 

Financiranje / Funding: Hrvatska zaklada za znanost / Croatian Science Foundation

 

VODITELJ PROJEKTA / PRINCIPAL INVESTIGATOR: izv. prof. dr. sc. Ivana Biljan

 

INSTITUCIJE KOJE SUDJELUJU U PROJEKTU / INSTITUTIONS:

Prirodoslovno-matematički fakultet Sveučilišta u Zagrebu / Faculty of Science at University of Zagreb (UniZg)

Institute of Organic Chemistry and Biochemistry, Prag / Institute of Organic Chemistry and Biochemistry, Prague

 

SAŽETAK:

Modularni dizajn odozdo prema gore, odnosno pristup povezivanja molekularnih građevnih jedinki unaprijed određene geometrije i funkcionalnosti na predvidljiv način, važan je put prema funkcionalnim organskim arhitekturama. U ovom projektu, osnovna ideja je upotrijebiti strukturno slične molekularne građevne jedinke, aromatske spojeve s dušikom, za dizajn samoudruženih višeslojeva i 2D polimera na čvrstim površinama s mogućom primjenom u molekularnoj elektronici, te za sintezu poroznih organskih materijala koji bi se mogli koristiti za adsorpciju i pohranjivanje plinova.

Aromatski C-nitrozo spojevi izloženi na međupovršini metal-otopina koristit će se kao predlošci za hijerarhijsku izgradnju azodioksidnih višeslojeva interakcijama s aromatskim dinitrozo derivatima. Mehanizam nastajanja i kinetika rasta nitrozo/azodioksidnih slojeva na površinama istražit će se elipsometrijom, AFM i STM mikroskopijom te računalnim metodama. Nadalje, provest će se in situ EC-STM istraživanja od kojih se očekuje pružanje informacija o strukturi i dinamici na razini pojedinačnih molekula. Također će se istražiti polimerizacija aromatskih polinitrozo derivata na površinama i moguće nastajanje površinom ograničenih 2D azodioksidnih polimera. Kristalni (COF-ovi) ili amorfni (COP-ovi) porozni organski materijali mogu nastati povezivanjem organskih građevnih jedinki preko kovalentnih veza. Aromatske građevne jedinke s nitrozo, nitro i/ili amino skupinama bit će korištene za modularni dizajn azo, azoksi i azodioksidnih COF-ova i/ili COP-ova. Strukturna i funkcionalna svojstva poroznih materijala bit će karakterizirana spektroskopijom, termičkom analizom, rentgenskom difrakcijom, mjerenjima specifične površine i molekularnim modeliranjem. Cilj je ispitati utjecaj različitih dušik-dušik veza na strukturna (kristalne naspram amorfnih krutina) i funkcionalna svojstva konačnih materijala te identificirati obećavajuće nove porozne sustave za učinkovito hvatanje CO₂, glavnog stakleničkog plina.

 

ABSTRACT:

A bottom-up modular design, an approach of piecing together molecular building blocks of predetermined geometry and functionality in a predictable manner, is an important route toward the functional organic architectures. Within this project, the basic idea is to employ structurally similar molecular building blocks, nitrogen-containing aromatic compounds, for a design of self-assembled multilayers and 2D polymers on solid surfaces with possible applications in molecular electronics, and for the synthesis of porous organic materials which could be used in gas adsorption and storage.

Aromatic C-nitroso groups exposed at the metal-solution interface will be used as templates for hierarchical construction of azodioxy multilayers by interactions with aromatic dinitroso derivatives. Formation mechanism and growth kinetics of nitroso/azodioxy adlayers on surfaces will be explored by ellipsometry, AFM and STM microscopy, and computational methods. In addition, in situ EC-STM studies expected to provide structure and dynamics information at single-molecule level will be performed. Polymerization of aromatic polynitroso compounds on surfaces and possible formation of surface-confined 2D azodioxy polymers will be also investigated. Crystalline (COFs) or amorphous (COPs) porous organic materials can be formed by linking organic building units through covalent bonds. Aromatic building blocks with nitroso, nitro and/or amino groups will be utilized for modular design of azo, azoxy and azodioxy COFs and/or COPs. Structural and functional features of porous materials will be characterized by spectroscopy, thermal analysis, X-ray diffraction, surface area measurements and molecular modelling. The aim is to examine the effect of different nitrogen-nitrogen linkages on structural (crystalline vs. amorphous solids) and functional properties of final materials and to identify the promising new porous organic systems for the effective capture of CO₂, the main greenhouse gas.

 

PROJEKTNI TIM / PROJECT TEAM:

Hrvoj Vančik

Vesna Petrović Peroković

Ivan Kodrin

Nikola Cindro

Željka Car

Igor Rončević

Mladen Borovina

Barbara Panić

Petar Šutalo

Laura Nuić

 

 

Znanstveni radovi / publications:

1. B. Panić, M. Koprivnjak, T. Marić, K. Majerová Varga, I. Biljan, The growth of nitrosobenzene adlayers on an Au(111) surface: The effect of experimental parameters, Colloid Interface Sci. Commun. 2021, 45, 100539, doi: 10.1016/j.colcom.2021.100539

 

2. K. Varga, H. Vančik, Z. Mihalić, Experimental and Theoretical IR Spectra of 2-Nitrosopyridines, Croat. Chem. Acta, 2020, 93(4), 337–345, doi: 10.5562/cca3820

 

3. L. Matasović, B. Panić, M. Bubaš, H. Vančik, I. Biljan, I. Rončević, Modulating electronic properties of dinitrosoarene polymers, J. Mater. Chem. C, 2022, 10, 5433–5446, doi: 10.1039/d2tc00760f

• Rad je zbog visoke ocjene recenzenata istaknut na naslovnici časopisa (Front Cover), te je uvršten u kolekciju „vrućih radova“ (HOT papers) za 2022. godinu.

  

   

 

 

 

4. P. Šutalo, M. Pisačić, I. Biljan, I. Kodrin, Benzene and triazine-based porous organic polymers with azo, azoxy and azodioxy linkages: a computational study, CrystEngComm, 2022 ,24, 4748–4763, doi: 10.1039/D2CE00186A

 

5. B. Panić, T. Frey, M. Borovina, K. Konopka, M. Sambolec, I. Kodrin, I. Biljan, Synthesis and Characterization of Benzene- and Triazine-Based Azo-Bridged Porous Organic Polymers, Polymers, 2023, 15, 229, doi: 10.3390/polym15010229

 

6. L. Nuić, B. Panić, L.-K. Pereković, I. Šrut Rakić, M. Kralj, A. Mihanović, H. Vančik, I. Biljan, Polymerization of aromatic dinitroso derivatives initiated by nitroso-terminated monolayer on Au(111) surface: Insights from ellipsometry, AFM and nano-FTIR spectroscopy, Polymer, 2023, 271, 125795, doi: 10.1016/j.polymer.2023.125795.

 

 

7. T. Frey, B. Panić, P. Šutalo, M. Borovina, I. Biljan, I. Kodrin, Prediction of CO₂ adsorption properties of azo, azoxy and azodioxy-linked porous organic polymers guided by electrostatic potential, CrystEngComm, 2023, 25, 3870. doi: 10.1039/D3CE00377A.

• Rad je zbog visoke ocjene recenzenata istaknut na naslovnici časopisa.

 

 

8. N. Cindro, Ž. Car, V. Petrović Peroković, M. Borovina, B. Panić, I. Kodrin, I. Biljan, Synthesis of aromatic polynitroso compounds: Towards functional azodioxy-linked porous polymers, Heliyon, 2023, 9, e21781. doi: 10.1016/j.heliyon.2023.e21781.

 

 

 

Sudjelovanje na skupovima / Conference participation:

1. B. Panić, M. Koprivnjak, T. Marić, I. Biljan, Influence of structural and experimental parameters on self-assembly of nitrosobenzene derivatives on gold surface, PhD Student Symposium PMF 2021, Zagreb, April 24–25, 2021 (poster).

2. B. Panić, I. Kodrin, I. Biljan, Design and characterization of azo-linked porous organic polymers, Solid-State Science & Research 2021, Zagreb, June 10–11, 2021 (poster).

3. B. Panić, K. Konopka, I. Biljan, Insights Into Structural Features of Azo-bridged Porous Organic Polymers by Using Solid-state NMR Spectroscopy, Adriatic NMR Conference, Primošten, September 13–15, 2021 (poster).

4. I. Biljan, Porous organic polymers with nitrogen functionalities: design and characterization, Adriatic NMR Conference, Primošten, September 13–15, 2021 (pozvano predavanje).

5. B. Panić, M. Koprivnjak, T. Marić, I. Biljan, Study of the growth process of nitrosobenzene adlayers on gold surface, 27HSKIKI, Veli Lošinj, October 5–8, 2021 (poster).

6. P. Šutalo, B. Panić, I. Biljan, I. Kodrin, Nitrogen-containing covalent organic polymers: Synthesis, characterization and computational study, 27HSKIKI, Veli Lošinj, October 5–8, 2021 (poster).

7. I. Kodrin, P. Šutalo, B. Panić, I. Biljan, Computational study of nitrogen-containing covalent organic polymers, 27HSKIKI, Veli Lošinj, October 5–8, 2021 (usmeno priopćenje).

8. L. Nuić, B. Panić, L. K. Pereković, I. Biljan, Design and characterization of azodioxy multilayers on gold surface, PhD Student Symposium PMF 2022, Zagreb, April 23–24, 2022 (poster).

9. B. Panić, M. Sambolec, I. Biljan, NMR insights into the structural features of triazine-based porous organic polymers, Magnetic Moments in Central Europe 2022, Primošten, June 1–4, 2022 (poster).

10. Ž. Car, N. Cindro, V. Petrović Peroković, B. Panić, I. Kodrin, I. Biljan, Synthesis, characterization and polymerization of aromatic trinitroso compounds, 8th EuChemS Chemistry Congress, Lisabon, Portugal, August 28–September 1, 2022 (poster).

11. I. Kodrin, I. Biljan, Rational design of porous organic materials based on azo, azoxy and azodioxy linkages for the selective adsorption of CO₂ over N₂, 8th EuChemS Chemistry Congress, Lisabon, Portugal, August 28–September 1, 2022 (usmeno priopćenje).

12. B. Panić, L. Nuić, I. Šrut Rakić, M. Kralj, I. Biljan, Self-Assembly, Dimerization and Polymerization of Aromatic C-Nitroso Derivatives on Gold Surface, V Symposium on Supramolecular Chemistry, Zagreb, December 8, 2022 (usmeno priopćenje).

13. B. Panić, I. Biljan, I. Kodrin, Synthesis and characterization of porous organic polymers with different organic building units bridged by azo bonds, 28HSKIKI, Rovinj, March 28–31, 2023 (usmeno priopćenje).

14. I. Biljan, L. Nuić, B. Panić, I. Šrut Rakić, M. Kralj, Insights into the polymerization of aromatic dinitroso derivatives initiated by nitroso-terminated monolayer on Au(111) surface, 28HSKIKI, Rovinj, March 28–31, 2023 (poster).

15. I. Kodrin, T. Frey, P. Šutalo, B. Panić, I. Biljan, Pyridine and amine-based porous organic materials with azo, azoxy and azodioxy linkages for selective CO₂ adsorption, 28HSKIKI, Rovinj, March 28–31, 2023 (poster).

16. V. Petrović Peroković, Ž. Car, N. Cindro, B. Panić, I. Kodrin, I. Biljan, Synthesis and characterization of aromatic trinitroso compounds – potential building blocks for new porous organic polymers, 28HSKIKI, Rovinj, March 28–31, 2023 (poster).

17. L. Nuić, B. Panić, I. Šrut Rakić, M. Kralj, H. Vančik, I. Biljan, Self-assembly and interactions of aromatic C-nitroso derivatives on Au(111) surface: from nitroso monolayers to azodioxy polymer films, Self-Assembly and Supramolecular Chemistry Gordon Research Conference, Les Diablerets, Švicarska, May 14–19, 2023 (poster).

18. L. Nuić, B. Panić, I. Šrut Rakić, M. Kralj, I. Biljan, Polymerization of aromatic C-nitroso derivatives on Au(111) surface: ellipsometry, AFM and nano-FTIR study, Solid-State Science & Research Meeting, Zagreb, June 28–30, 2023 (usmeno priopćenje).

19. B. Panić, I. Kodrin, I. Biljan, Azo-bridged porous organic polymers based on benzene, triazine and pyridine building units, 5th European Conference on Metal Organic Frameworks and Porous Polymers, Granada, Španjolska, September 24–27, 2023 (poster).

20. I. Kodrin, I. Biljan, M. Đaković,  Periodic DFT Calculations in the Design of Functional Materials, VI Symposium on Supramolecular Chemistry, Zagreb, December 6, 2023 (pozvano predavanje).

21. L. Nuić, B.Panić, I. Šrut Rakić, M. Kralj, I. Biljan, From self-assembled monolayers and bilayers of aromatic C-nitroso derivatives to azodioxy polymer films on gold surface, VI Symposium on Supramolecular Chemistry, Zagreb, December 6, 2023 (usmeno priopćenje).

22. L. Nuić, B.Panić, I. Šrut Rakić, M. Kralj, I. Biljan, Insights into the self-assembly and interactions of aromatic C-nitroso derivatives on gold surface, European Winter School on Physical Organic Chemistry, Bressanone, Italy, February 4–9, 2024 (poster).

 

Nagrade / Awards:

1. Lujo Matasović (mentor:  izv. prof. dr. sc. Ivana Biljan; neposredni voditelj: dr. sc. Igor Rončević)

• Ugađanje optoelektričkih svojstava derivata di- i trinitrozoarena / Tuning optoelectronic properties of di- and trinitrosoarene derivatives, Rector's award for the best students projects in 2020/2021

 

Diplomski radovi / Diploma theses:

1. Miro Sambolec (mentor: izv. prof. dr. sc. Ivana Biljan)

• Sinteza i karakterizacija azo-premoštenih kovalentnih organskih polimera sa središnjom triazinskom jedinicom, Diplomski rad, Zagreb, 24.9.2021.

• Synthesis and characterization of azo-bridged covalent organic polymers with triazine central unit, Diploma Thesis, Zagreb, September 24, 2021

2. Lovorka-Kristina Pereković (mentor: izv. prof. dr. sc. Ivana Biljan)

• Istraživanje nastajanja azodioksidnih višeslojeva na površini zlata mikroskopijom atomskih sila, Diplomski rad, Zagreb, 25.2.2022.

• Study of formation of azodioxy multilayers on gold surface by atomic force microscopy, Diploma Thesis, Zagreb, February 25, 2022.

3. Tea Frey (mentor: izv. prof. dr. sc. Ivan Kodrin)

• Strukturna i adsorpcijska svojstva azo, azoksi i azodioksidnih poroznih organskih polimera izvedenih iz trisupstituiranog amina i piridina, Diplomski rad, Zagreb, 21.2.2023.
• Structural and adsorption properties of azo, azoxy and azodioxy porous organic polymers derived from trisubstituted amines and pyridines, Diploma Thesis, Zagreb, February 21, 2023.

4. Petra Ištoković (mentror:  izv. prof. dr. sc. Ivana Biljan)

• Porfirinski i adamantanski porozni organski polimeri s azo poveznicama, Diplomski rad, Zagreb, 21.12.2023.
• Porphyrinic and adamantane porous organic polymers with azo linkages, Diploma Thesis, December 21, 2023

5. Ena Asić (mentror:  izv. prof. dr. sc. Ivana Biljan)

• Sinteza novih aromatskih C-nitrozo derivata i njihova adsorpcija na površinu zlata, Diplomski rad, Zagreb, 22.2.2024.
• Synthesis of new aromatic C-nitroso derivatives and their adsorption on gold surface, Diploma Thesis, February 22, 2024.