PROJEKT  FlexibleCrystals

IP-2019-04-1242

Trajanje / Duration:

15.01.2020. - 14.02.2024.

Financiranje / Funding:

HRVATSKA ZAKLADA ZA ZNANOST

VODITELJ PROJEKTA / PRINCIPAL INVESTIGATOR:

Izv. prof. dr. sc. Marijana Đaković

INSTITUCIJE / INSTITUTIONS:

Sveučilište u Zagrebu, Prirodoslovno-matematički fakultet / University of Science, Faculty of Science

Sveučilište u Splitu, Kemijsko-tehnološki fakultet / University of Split, Faculty of Chemistry and Technology

Kansas State Univesity

NAZIV PROJEKTA / PROJECT TITLE:

Od oblika do funkcije: Fleksibilni kristalni materijali s kontroliranim mehaničkim odzivom

From form to function: Mechanically flexible crystalline materials with controllable responses

SAŽETAK / ABSTRACT:

Mehanička savitljivost, iako osnovno svojstvo većine živih sustava, rijetko se pojavljuje kod kristalnih materijala. Kristalne krutine općenito su nesavitljive i lako pucaju i/ili se lome pri izlaganju mehaničkom podražaju, osobito ako su im građevne jedinke povezane međumolekulskim interakcijama usporedive jakosti u svim smjerovima. Međutim, nekoliko nedavno objavljenih znanstvenih radova opisuje savitljive organske kristale i svega nekoliko primjera 0-D metaloorganskih kristalnih krutina koje mogu pokazivati savitljivost pod utjecajem mehaničke sile. Prvi rad o mehanički savitljivim kristalnim 1-D koordinacijskim polimerima objavljen je 2018. godine. U tom radu smo pokazali da se stupanj elastičnosti može kontrolirati uvođenjem malih ali kontroliranih strukturnih promjena, a takvo nešto dosad još nije bilo poznato.
S ciljem potpunog razumijevanja i objašnjenja uvjeta potrebnih za prilagodljivost i ugodivu savitljivost kristalnih koordinacijskih polimera pod utjecajem vanjskog mehaničkog podražaja, predlažemo kombinaciju teorije i eksperimenta za sustavno istraživanje specifičnih strukturnih značajki i međumolekulskih interakcija te njihovog utjecaja na mehanička svojstva kristalnih koordinacijskih polimera. Glavni je cilj ovog interdisciplinarnog istraživanja na granici kemije i znanosti o materijalima definirati postojane i prenosive smjernice za dizajn kristalnih koordinacijskih polimera s a priori određenom savitljivošću, na temelju ‘bottom-up’ pristupa. Takvi materijali imali bi najbolja svojstva meke i kristaline tvari – ugodivu pokretljivost i očuvanu uređenost dalekog dosega. Time bi pružili nove i jedinstvene mogućnosti znanosti o materijalima i inženjerstvu, jer navedeni koordinacijski polimeri omogućuju dosad nezamisliv uvid u novu generaciju pametnih materijala s ugodivom funkcijom.

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Mechanical flexibility, an essential characteristic of most living systems, is rare among crystalline materials. Crystalline solids are in general brittle, and they tend to crack and/or break upon application of mechanical stress, especially if they are held together by intermolecular bonds that are of comparable strength in all directions. Recently, however, there have been several reports of flexible organic crystals, and a few cases of 0-D metal-organic crystalline solids that can respond flexibly to an applied mechanical force. The very first paper on crystalline 1-D coordination polymers with mechanical flexibility was published in 2018, wherein we also demonstrated that the extent of elasticity could be controlled by introducing small and controllable structural modifications, something that had not been accomplished before.
In order to fully understand and explain which conditions need to be met for crystalline coordination polymers to be adaptive and tunably flexible in response to external mechanical stimuli, we propose a combination of theory and experiment to systematically explore how specific structural features and intermolecular interactions impart mechanical properties in crystalline coordination polymers. The overarching goal of this interdisciplinary research effort at the interface of chemistry and materials science is to deliver robust and transferable guidelines for bottom-up design of coordination polymers with a priori determined flexibility.  Such materials would combine the best features of both soft and crystalline matter, by presenting tunable mobility whilst preserving a long-range order, and subsequently offer unique opportunities for materials science and engineering as they contain coordination polymers at their core, which can provide unprecedented access to a new generation of smart materials with tunable functionality.

PROJEKTNI TIM / PROJECT TEAM:

PMF: Ivana, Biljan, Mladen Borovina, Ivan Kodrin, Ozana Mišura,
          Mateja Pisačić, Željka Soldin, Marko Pužar

KTF:  Boris-Marko Kukovec

KSU: Viraj de Silva, Christer B. Aakeröy

Znanstveni radovi / publications:

1. M. Pisačić, I. Biljan, I. Kodrin, N. Popov, Ž. Soldin, M. Đaković, Elucidating the origins of a range of diverse flexible responses in crystalline coordination polymers, Chem. Mater. 2021, 33, 10, 3660–3668, doi: 10.1021/acs.chemmater.1c00539

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

2 .M. Pisačić, I. Kodrin, I Biljan, M. Đaković, Exploring the diversity of elastic responses of crystalline cadmium(II) coordination polymers: From elastic towards plastic and brittle responses, CrystEngComm, 2021, 23, 7072-7080.

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

3. M. Pisačić, I. Kodrin, A. Trninić, M. Đaković, Two-Dimensional Anisotropic Flexibility of Mechanically Responsive Crystalline Cadmium(II) Coordination Polymers, Chem. Mater., 2022, 34, 2439-2448.

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

4. O.Mišura, M. Pisačić, M. Borovina, M. Đaković, Tailoring enhanced elasticity of Crystalline Coordination Polymers, Cryst. Growth & Des., 2023, 3, 1318-1322.

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

5. O.Mišura, I. Kodrin, M. Borovina, M. Pisačić, V. De Silva, C. B. Aakeröy, M. Đaković, Exploring the co-crystalization landscape of 1-D coordination polymers using an MEP-driven approach, Cryst. Growth & Des., doi: 10.1021/acs.cgd.3c00615

Sudjelovanje na skupovima / Conference participation:

1. M. Đaković, M. Pisačić, Impact of Halides and Halogen Atoms on Mechanical Flexibility of Cd(II) Coordination Polymers, 4th International Symposium on Halogen Bonding, Virtual Event form Stellenbosch, South Africa, 2-5 November, 2020 (prerecorded oral presentation)
2. M. Pisačić, M. Đaković, Kristali koordinacijskih polimera kadmija(II) s mehanički potaknutim fleksibilnim odzivom / Crystals of cadmium(II) polymers with mechanically induced flexibilty, 4th Faculty of Science PhD Students Symposium, Zagreb, February 28, 2020 (oral presentation)
3. L. Čolakić, M. Pisačić, M. Đaković, Mechanically responsive crystals of cadmium(II) halides with oxime derivatives of pyridine, XIII Meeting of Young Chemical Engineers, Zagreb, 20-21 February, 2020 (oral presentation)
4. O. Mišura, M. Pisačić, M. Đaković, Modulatin mechanical flexibilty of cadmium(II) coordination compounds via co-crystallization, 5th PhD Student Symposium PMF, Zagreb, April 24-25, 2021 (poster presentation)
5. L. Čolakić, M. Pisačić, M. Đaković, Fine-tunning of mechanical flexibility of cadmium(II) halide crystals via ligand replacement, Solid-State Science & Research, Zagreb, Jun 10-11, 2021 (poster presentation)
6. M. Đaković, M. Pisačić, Variable adaptability of crystalline coordination polymers of cadmium(II) to external mechanical stimuli, IUCr Congress and General Assembly, Prague, August 14-22, 2021 (invited lecture)
7. M. Pisačić, M. Đaković, Tuning mechanical responses of crystalline cadmium(II) coordination polymers through cyano functionality and halide anions, IUCr Congress and General Assembly, Prague, August 14-22, 2021 (oral presentation)
8. M. Đaković, Mechanically responsive moecular crystals, XLIX Meeting of the Italian Crystallographic Association (AIC), Parma, September 6-8, 2021 (plenary lecture)
9. M. Pisačić, M. Đaković, Crystaline coordination polymers on the move, 27HSKIKI, Veli Lošinj, October 5-8, 2021 (oral presentation)
10. M. Đaković, Can mechanical responses of flexible crystals be controlled and deliberately delivered? 27HSKIKI, Veli Lošinj, October 5-8, 2021 (oral presentation)
11. M. Borovina, M. Pisačić, A. Husinec, V. Badurina, M. Đaković, Mechanical properties of copper(II) and cadmium(II) halides equipped with 3-nitropyridine ligands, 27HSKIKI, Veli Lošinj, October 5-8, 2021 (poster presentation)
12. O. Mišura, M. Đaković, Co-crystals of Cd(II) coordination polymers with simple organic compounds, 27HSKIKI, Veli Lošinj, October 5-8, 2021 (poster presentation)
13. Ž. Soldin, M. Pisačić, K. Zozoli, M. Đaković, Elastically deformable crystals of Cd(II) coordination polymers, 27HSKIKI, Veli Lošinj, October 5-8, 2021 (poster presentation)
14. M. Borovina, M. Pisačić, A. Husinec, A. Badurina, M. Đaković, Investigating the impact of supramolecular connectivity on mechanical properties of crystals, IV Simpozij supramolekulske kemije, Zagreb, December 10, 2021 (oral presentation)
15. L. Čolakić, M. Pisačić, M. Đaković, Mehanička svojstva kristala kadmijevih(II) halogenida s 2,6-dibrompirazinskim ligandima, IV Simpozij skupramolekulske kemije, Zagreb, December 10, 2021 (poster presentation)
16. L. Čolakić, M. Pisačić, M. Đaković, Fleksibilni kristali kadmijevih(II) halogenida s diklorpiridinskim ligandima, XIV SMLKI, Zagreb, February 24-25, 2022 (oral presentation)
17. A. Mihal, O. Mišura, M. Đaković, Mehanički potaknuta fleksibilnost kristala koordinacijskih polimera bakra(II), XIV SMLKI, Zagreb, February 24-25, 2022 (poster presentation)
18. O. Mišura, M. Đaković, Mechanical behaviour of crystals of copper(II) coordination polymers, 6th PhD Student Symposium PMF, Zagreb, April 23-24, 2022 (oral presentation)
19. M. Đaković, A maze of crystal adaptability, ICCOSS XXV, Ohrid, Macedonia, July 3-8, 2022 (invited presentation)
20. M. Pisačić, L. Balen, M. Đaković, A walk through the valley of weak interactions and diverse mechanical responses of crystals, ECM33, Versailles, August 23-27, 2022 (oral presentation)
21. M. Đaković, M. Pisačić, O. Mišura, Mechanically responsive crystals: Tuning flexibility through fine-tuning intermolecular interactions, ECM33, Versailles, August 23-27, 2022 (oral presentation)
22. O. Mišura, M. Đaković, Variability of mechanical responsiveness of crystals of copper(II) halides with a family of pyridine-based ligands, CSCM28, Poreč, September 7-11, 2022 (oral presentation)
23. M. Đaković, Crystals’ adaptability to external mechanical stimuli: Structural causes and consequences, CSCM28, Poreč, September 7-11, 2022 (oral presentation)
24. M. Pisačić, B. Lovrić, M. ĐAković, Shaping crystals using mechanical force: A structural perspective on flexible crystalline coordination polymers of cadmium(II), 4th joint AIC-SILS, Trieste, September 12-15, 2022 (oral presentation)
25. L. Čolakić, M. Pisačić, M. Đaković, Dual stress - Mechanical properties of copper(II) crystals with 3-nitropyridine, SiSK7, Zagreb, October 22, 2022 (oral presentation)
26. M. Đaković, The Role of Halogen and Hydrogen Bonds in Delivery of Flexible Crystals with Targeted Mechanical Response, ISXB5, Tokyo, November 6-10, 2022 (invited presentation)
27. L. Čolakić, M. Pisačić, M. Đaković, Electrical Properties of Flexible Coordination Compounds of Copper(II) Halides with 3-nitropiridine, 5th SupramolChem, Zagreb, December 8, 2022 (oral presentation)
28. L. Komučar, M. Pisačić, M. Đaković, Utjecaj kationa metala na mehničkim putem izazavanu savitljivost kristala na primjeru koordinacijskih polimera kadmijevih(II) i bakrovih(II) halogenida s 3,5-lutidinom, 5th SupramolChem, Zagreb, December 8, 2022 (poster presentation)
29. O. Mišura, M. Đaković, Crystal of copper(II) coordination polymer with mechanically and thermally induced motions, 7th PhD Student Symposium PMF, Zagreb, April 21-22, 2023 (oral presentation)
30. M. Đaković, Mechanically flexible crystalline coordination polymers: What do we know about the crystals' mechanically induced adaptability? SCCM29, Topolšica, June 14-18, 2023 (oral presentation)
31. M. Borovina, M. Đaković, Crystallography on the verge - Solving crystal structures of bent crystals. SCCM29, Topolšica, June 14-18, 2023 (oral presentation)
32. M. Pisačić, L. Čolakić, B. Lovrić, M. Đaković, The power of weak intermolecular interactions in achieving the specific flexible response, ECS8, Berlin, June 18-24, 2023 (poster presentation)
33. O. Mišura, M. Đaković, Mechanically compliant crystals of copper(II) bromide equipped with halogen-pyrazine: elucidating the effect of halogen atom substitution, ECS8, Berlin, June 18-24, 2023 (poster presentation)
34. L. Komočar, M. Pisačić, I. Kodrin, M. Đaković, Computational and structural studies of flexible coordination polymers of copper(II) and cadmium(II). SciRes, Zagreb, June 28-30, 2023 (poster presentation)
35. L. Čolakić, M. Pisačić, A. Šantić, M. Đaković, Investigation the properties of flexible copper(II) crystals containing 3-nitropyridine ligands, SciRes, Zagreb, June 28-30, 2023 (poster presentation)
36. M. Pisačić, M. Đaković, Dancing crystals - mechanically and thermally stimulated crystal movements, SciRes, Zagreb, June 28-30, 2023 (oral presentation)

Nagrade / Awards:

1. M. Đaković, Godišnja Državna nagrada za znanost / Annual Science Award by Republic of Croatia, 2022
2. M. Pisačić, Godišnja nagrada za znanost Prirodoslovno-matematičkog fakulteta / Annual Science Award of the Faculty of Science, 2022
3. M. Borovina, Poster prize
   Mechanical properties of copper(II) and cadmium(II) halides equipped wiht 3-nitropyridine ligands
   27HSKIKI, Veli Lošinj, October 5-8, 2021
4. Mateja Pisačić, Best Oral Presentation award
   Kristali koordinacijskih polimera kadmija(II) s mehanički potaknutim fleksibilnim odzivom / Crystals of cadmium(II) polymers with mechanically induced flexibilty,
   4th Faculty of Science PhD Students Symposium, Zagreb, February 28, 2020
5. Mateja Pisačić, Best Poster Prize
   M. Pisačić, L. Komočar, M. Đaković, The power of weak intermolecular interactions in achieving the specific flexible response, ECS8, Berlin, June 18-24, 2023
6. Mateja Pisačić, Best Poster Prize
   M. Pisačić, B. Lovrić, M. Đaković, Jumping between different crystal forms – a structural perspective on stimuli-initiated crystals’ movements, 12th Crystal Forms, Bologna, September 10-12, 2023
7. Ozana Mišura, The best oral presentation award,
   Kristali koordinacijkog polimera bakra(II) s mehanički i termički induciranom pokratljivošću / Crystals of copper(II) coordination polymer with mechanically and thermally induced motions, 
   4th Faculty of Science PhD Students Symposium, Zagreb, April 21, 2023
8. Lea Čolakić, Rector's award
   Elastičnost kristala kadmijevih(II) polimera s halogenidnim i piridinkarboksimskim ligandima / Elasticity of cadmium(II) polymer crystals with halide and pyridinecarboxamide ligands (3rd year undergraduate student)
   Rector's award for the best students projects in 2019/2020
9. Božena Lovrić, Rector's award
   Mehanički odziv kristala kadmijevih(II) halogenida s dihalogenpiridinskim ligandima/Mechanically reponsive cadmium(II) halides with dihalogenpyridine ligands (3rd year undergraduate student)
   Rector's award for the best students projects in 2020/2021
10. Tea Frey, Rector's award
    Računalno istraživanje supramolekulskih interakcija u elastičnim koordinacijskim polimerima kadmijevih(II) halogenida s pirazinamidom / Computational investigation of supramolecular interactions in elastic coordination polimers of cadmium(II) halides with pyrazinamide
    Rector's award for the best students projects in 2020/2021
11. Lea Čolakić, Nagrada Fonda Nenada
    Nagrada Fonda Nenada M. Kostića za njabolje diplomske radove
    Električna i termička svojstva fleksibilnih kristala koordinacijskih polimera bakrovih(II) halogenida s 3-nitropiridinom, Diplomski rad, Zagreb, 14.11.2022. (mentori: M. Đaković, A. Šantić)
12. Ozana Mišura,The best oral presentation award,
    O. Mišura, M. Đaković, Crystal of copper(II) coordination polymer with mechanically and thermally induced motions
    7th Faculty of Science PhD Students Symposium, Zagreb, April 21-23, 2023
13. Lea Komočar, Rector's award
    Računalno i strukturno istraživanje savitljivosti kristala koordinacijskih spojeva bakrovog(II) i kadmijevog(II) bromida s 3,5-lutidinom
    Rector's award for the best students projects in 2022/2023
14. Mateja Pisačić, Best Poster Award
    M. Piscačić, B. Lovrić, M. Đaković, Jumping between different crystal forms - a structure perspective on stimuli-initiate crystals' movements
    12th Bologna’s convention on crystal forms, Bologna, September 10-12, 2023

Obranjene doktorske disertacije / Doctoral Theses defended:

1. Mateja Pisačić

• Mechanicall flexible crystals of cadmium(II) coordination polymers, Doctoral Dissertation, Zagreb, November 24, 2022
• Kristali koordinacijskih polimera kadmija(II) s mehanički potaknutim fleksibilnim odzivom, Doktorska disertacija, Zagreb, 24.11.2022.

Obranjeni diplomski radovi / Diploma Theses defended:

1. Valentina Badurina

• Fleksibilnost jediničnih kristala koordinacijskih spojeva bakrovih(II) halogenida s 3-nitropiridinom, Diplomski rad, Zagreb, 24.02.2020.

• Flexibility of singlecrystals of copper(II) halogenide coordination compounds with 3-nitropyridine, Diploma Thesis, Zagreb, February 24, 2020

2. Ozana Mišura

• Priprava kokristala koordinacijskih polimera kadmija(II): Utjecaj steričkih i elektronskih efekata na nastanak i održivost njihovih struktura, Diplomski rad, Zagreb, 21.02.2020.
• Preparation of co-crystals of cadmium(II) coordination polymers: Impact of steric and electronic effects on the formation and sustainability of their structure, Diploma Thesis, Zagreb, February 21, 2020

3. Ana Husinec

• Istraživanje mehaničkog odziva kristala kadmijevih(II) halogenida s 3-nitropiridinom, Diplomski rad, Zagreb, 20.02.2020.

• Exploring mechanical responses of cadmium(II) halides with 3-nitropyridine, Diploma Thesis, Zagreb, February 20, 2020

4. Karla Zozoli

• Mehanički savitljivi kristali koordinacijskih polimera kadmijevih(II) halogenida s 2(1H)-pirazinonom i 4(3H)-pirimidinonom, Diplomski rad, Zagreb, 14.07.2021.
• Mechanically flexible crystals of cadmium(II) halide coordination polymers with 2(1H)-pyrazinone i 4(3H)-pyrimidinone, Diploma Thesis, Zagreb, July 14, 2021

 5. Antonija Volmut 

• Koordinacijski polimeri bakrovih(II) halogenida s amidnim derivatima piridina i pirazina: kristali fleksibilnog mehaničkog odziva, Diplomski rad, Zagreb, 28.09.2021.
• Copper(II) halide coordination polymers with the amide derivatives of pyridine and pyrazine: crystals displaying flexible mechanical responses, Diploma Thesis, Zagreb, September 28, 2021

6. Luka Balen

• Utjecaj strukturnih značajki na mehaničku savitljivost kristala jednodimenzijskih koordinacijskih polimera kadmijevih(II) halogenida s derivatima piridina i pirazina, Diplomski rad, Zagreb, 25.02.2022.
• Impact of structural features on mechanical flexibility of crystals of one-dimensional cadmium(II) polymers with halides and pyridine and pyrazine derivatives, Diploma Thesis, Zagreb, February 25, 2022

7. Andrea Mihal

• Ispitivanje mehaničkog odziva kristala bakrovih(II) halogenida s metilnim derivatima piridina, Diplomski rad, Zagreb, 14.04.2022.
• Exploring mechanical responsiveness of crystals of cooper(II) halides and methyl derivatives of pyridine, Diploma Thesis, Zagreb, April 14, 2022

8. Antonia Vardian

• Primjena termičke analize i Ramanove mikroskopije u istraživanju fleksibilnosti kristala koordinacijskih polimera kadmijevih(II) halogenida s halogeniranim piridinima, Diplomski rad, Zagreb, 30.09.2022.
• Application of thermal analysis and Raman microscopy in the study of the flexibility of coordination polymers of cadmium(II)  halides with halogen substituted pyridines, Diploma Thesis, Zagreb, September 30, 2022

9. Marko Tomić

• Strukturno i računalno istraživanje supramolekuskih motiva u koordiancijskim spojevima bakra(II) s piridinoksimima, Diplomski rad, Zagreb, 30.09.2022.

• Structural and computational study od supramolecular motifs in coordination compounds of copper(II) with pyridineoximes, Diploma Thesis, Zagreb, September 30, 2022

10. Lea Čolakić

• Električna i termička svojstva fleksibilnih kristala koordinacijskih polimera bakrovih(II) halogenida s 3-nitropiridinom, Diplomski rad, Zagreb, 14.11.2022.
• Electric and thermal properties of flexible crystals of coordination polymers of copper(II) halogenides with 3-nitropyridine, Diploma Thesis, Zagreb, November 14, 2022

11. Marina Đukin