INNOVATION AND CREATIVITY

EXECUTIVE AGENCY FOR HIGHER EDUCATION,

RESEARCH, DEVELOPMENT AND INNOVATION FUNDING

EXPLORATORY RESEARCH PROJECTS

Contractor "Petru Poni" Institute of Macromolecular Chemistry, Romanian Academy

Project: PN-II-ID-PCE-2012-4-0261

Contract No. 53/02.09.2013

Project duration September 2013-September 2016

Granted by UEFISCDI

Project Director Dr. Maria Cazacu

The interface between inorganic and organic materials chemistry is an area that has been developing rapidly in recent years. Considerable work has been directed towards the synthesis of extended chemical networks which combine metal centers and organic ligands in such a way as to form coordination polymers, and often porous materials very useful for catalysis, microelectronics, nonlinear optics, gas purification and gas storage, magnetism, luminescence.

Metal-organic frameworks (MOFs) are considered as three-dimensionally connected networks comprising nodes, which are metal cations or di-, tri- or tetra-, or polynuclear metal cation clusters, linked by organic spacers, which are usually di-, tri- or tetradentate ligands.

When the coordination bonds between metals and ligands are strong, this gives rise to crystallographically well-defined open structures that are stable to the removal of guest molecules, giving permanent porosity. These porous MOFs are able to reversibly adsorb gases and vapours, sometimes in very large amounts that exceed by many times the specific adsorption capacities of even the most open zeolites.

The general objective of the project is to synthesize and fully characterize new metal-organic frameworks with highly flexible siloxane sequences as linkers and metallocentric building units.

Stage 2013 265.000,00Stage 2014 263.718,00Stage 2015 375.743,00Stage 2016 220.539,00Total Budget 1.125.000, 00

20131.Preparation of the polynuclear transition metal μ-oxo clusters2.Obtaining of the siloxane or silane compounds as structural building units (SBUs) of the metal-organic networks

20141.Obtaining of the siloxane or silane compounds as structural building units (SBUs) of the metal-organic networks2.Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands

20151.Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands (continued)2.Preparation of the extended networks having preformed or “in situ” formed metal clusters and the obtained siloxane or silane ligands

20161.Preparation of the extended networks having preformed or “in situ” formed metal clusters and the obtained siloxane or silane ligands 2.Evaluation of some properties and potential applications for the metal-silicone networks

1. A 2D metal-organic framework based on dizinc coordination units bridged through both flexible and rigid ligands, A. Vlad, M. Cazacu, M.F. Zaltariov, A. Bargan, S. Shova, C. Turta, J. Mol. Struct., 2014, 1060, 94-101.

2. Tetranuclear copper(II) complexes with macrocyclic and open-chain disiloxane containing ligands as catalyst precursors for hydrocarboxylation and oxidation of alkanes and 1-phenylethanol, M.F. Zaltariov, M. Alexandru, M. Cazacu, S. Shova, Gh. Novitchi, C. Train, A. Dobrov, M.V. Kirillova, E.C.B.A. Alegria, A.J.L. Pombeiro, V.B. Arion, Eur. J. Inorg. Chem. 2014, 29, 4946-4956.

3. Copper(II) complexes with 1,5-bis(2-hydroxybenzaldehyde) carbohydrazone, D. Dragancea, S. Shova, É.A. Enyedy, M. Breza, P. Rapta, L. M. Carrella, E. Rentschler, A. Dobrov, V. B. Arion, Polyhedron 2014, 80, 180–192.

4. Novel siloxane-containing dicarboxylic acid, 1,3-bis(p-carboxyphenylene-ester-methylene) tetramethyldisiloxane, and its derivatives: ester macrocycle and supramolecular structure with a copper complex, M.-F. Zaltariov, A. Vlad, M. Cazacu, S. Shova, M. Balan, C. Racles, Tetrahedron 2014, 70, 2661-2668.

5. Magnetic relaxation versus 3D long-range ordering in {Dy2Ba(α-fur)8}n furoate polymers, E. Bartolomé, Bartolomé, S. Melnic, D. Prodius, S. Shova, A. Arauzo, J. Luzón, L. Badía-Romano, F. Luis, C. Turta, Dalton Trans. 2014, 43, 10999–11013.

6. Di- and tetracarboxylic aromatic acids with silane spacers and their copper complexes: synthesis, structural characterization, and properties evaluation, M. Cazacu, A. Vlad, M.-F. Zaltariov, S. Shova, G. Novitchi, C. Train, J. Organometal. Chem. 2014, 774, 70-78.

7. Silicon-containing bis-azomethines: synthesis, structural characterization, evaluation of the photophysical properties and biological activity, M.-F. Zaltariov, A. Vlad, M. Cazacu, M. Avadanei, N. Vornicu, M. Balan, S.Shova, Spectrochim. Acta A–2015, 138, 38-48

8. Metallopolymers based on a polyazomethine ligand containing oxadiazole rigid and tetramethyldisiloxane flexible units, M.-F. Zaltariov, M. Cazacu, C. Racles, V. Musteata, A. Vlad, A. Airinei, J.Appl. Polym. Sci.- 2015, 132, 41631.

9. Coordination polymer of copper with a silicon-containing Schiff base: synthesis, structural characterization, properties, M. F. Zaltariov, M. Cazacu, A. Vlad, L. Sacarescu, S. Shova, High Perform. Polym. 2015, 27(5), 607–615.

10. Synthesis, characterization and antimicrobial activity of new Cu(II) and Zn(II) complexes with Schiff bases derived from trimethylsilyl-propyl-p-aminobenzoate, M. F. Zaltariov, M. Cazacu, M. Avadanei, S. Shova, M. Balan, N. Vornicu, A. Vlad, A. Dobrov, C. D. Varganici, Polyhedron 2015, 100, 121–131.

11. Charge and spin states in Schiff base metal complexes with a disiloxane unit exhibiting a strong noninnocent ligand character: synthesis, structure, spectroelectrochemistry, and theoretical calculations, M. Cazacu, S. Shova, A. Soroceanu, P. Machata, L. Bucinsky, M. Breza, P. Rapta, J. Telser, J. Krzystek, V. B. Arion, Inorg. Chem., 2015, 54 (12), 5691–5706.

12. Supramolecular aggregation in organic solvents of discrete copper complexes formed with organosiloxane ligands, A. Soroceanu, M. Cazacu, C. Racles, I. Stoica, L. Săcărescu, C. D. Varganici, Soft Mater. 2015, 13, 93-105.

13. Superparamagnetic amorphous iron oxide nanowires self-assembled into ordered layered structures, M. Iacob, D. Sirbu,C. Tugui, G. Stiubianu, L. Sacarescu, V. Cozan, A. Zeleňáková, E. Čižmár, A. Feher, M. Cazacu. RSC Advances 2015, 5, 62563-62570 .

14. Goethite nanorods as cheap and effective filler for siloxane nanocomposite elastomers, M. Iacob, G. Stiubianu, C. Tugui, E.L. Ursu, M. Ignat, C. I. Turta, M. Cazacu, RSC Advances 2015, 5, 45439-45446.

15. Amorphous iron–chromium oxide nanoparticles with long-term stability, M. Iacob, M. Cazacu, C. Turta, F. Doroftei, M. Botko, E. Čižmár, A. Zeleňáková, A. Feher, Materials Research Bulletin, 2015, 65, 163-168.

16. Sonochemical synthesis of hematite nanoparticles, M. Iacob, Chemistry Journal of Moldova, 2015, 1, 46-51.

17. Full functionalized silica nanostructure with well-defined size and functionality: Octakis(3-mercaptopropyl)octasilsesquioxane, C. Dumitriu, M. Cazacu, A. Bargan, M. Balan, N. Vornicu, C. D. Varganici, S. Shova, J. Organomet. Chem. 2015, 799-800, 195-200.

18. Synthesis and characterization of metal-containing poly(siloxane-urethane) crosslinked structures derived from siloxane diols and ferrocene diisocyanate, M. Dascalu, V. E. Musteata, L. Vacareanu, C. Racles, M. Cazacu, RSC. Advances 2015, DOI: 10.1039/C5RA15290A.

19. Design and synthesis of the first ferrocenylsiloxane urea: structure and properties, M. Dascalu, M. Balan, S. Shova, C. Racles, M. Cazacu, Polyhedron 2015, DOI:10.1016/j.poly.2015.11.013.

8. Des composites polysiloxane–complexes métalliques. Préparation et propriétés, Dumitriu, A.-M. C.; Bele, A.; Stiubianu, G.; Cazacu, M.; Racles, C.; Bargan, A., XIème Colloque Franco-Roumain sur les Polymères 27-29 August 2014, Pitesti, Romania-poster.

9. Optical properties and self-assembling capacity of metal-containing siloxane polyazomethines, Zaltariov, M.F.; Cazacu, M.; Racles, C.; Vlad, A.; Avadanei, M.; Hitruc, G.; Gradinaru, L.; Stiubianu, G.; Airinei, A., The 14-th International Balkan Workshop on Applied Physics, 2-4 Iulie 2014, Constanța, Romania.

10.Heterocyclic compounds with silicon and metal, Dumitriu,A.M.C.; Bargan, A.; Cazacu, M., The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova, 28- 30 Mai 2014, Chisinau, Moldova- poster

11. Silatranes functionalized with azomethine groups, Dumitriu, A.M.C.; Vlad, A.; Shova, S.; Cazacu, M., The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova, 28- 30 Mai 2014, Chisinau, Moldova-poster.

12. From iron clusters to iron oxides nanoparticles, Iacob, M.; Cazacu, M.; Racles, C.; Zgardan, C.; Cuzan, O.; Straistari, T.; Sacarescu, L.; Cozan, V.; Turta, C., The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova, 28- 30 Mai 2014, Chisinau, Moldova-poster.

13. Flexible and hydrophobic Zn-based coordination polymer: synthesis, structure, evaluation of the thermal and sorption properties, Vlad, A.; Cazacu, M.; Shova, S.; Turta, C.; Zaltariov, M.-F., The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova, 28- 30 Mai 2014, Chisinau, Moldova-poster.

14. Synthesis, structural characterization, photophysical and antimicrobial properties of new schiff bases containing dimethylsilane units, Zaltariov, M.F.; Avadanei, M.; Vornicu, N.; Cazacu, M.; Shova, S.; Vlad, A., The International Conference dedicated to the 55th anniversary from the foundation of the Institute of Chemistry of the Academy of Sciences of Moldova, 28- 30 Mai 2014, Chisinau, Moldova-poster.

15. Structural diversity in Cu(II) and Co(II) complexes induced by flexible ligands, Zaltariov, M., Cazacu, M., Shova, S., Seventh Cristofor I. Simionescu Symposium Frontiers in Macromolecular and Supramolecular Science 4-5 June, 2015, Iasi, Romania-oral presentation.

16. μ3-oxotrinuclear iron carboxy-clusters as effective alternative sources for their oxide nanoparticles. Iacob, M., Racles, C., Tugui, C., Stiubianu, G., Cazacu, M., 15th International Balkan Workshop on Applied Physics, Constanta, 2-4 June 2015 – oral presentation.

17. Managing silicone electromechanical properties through inorganic nanoparticles fillers. Iacob, M., Stiubianu, G., Tugui, C., Bele, A., Cazacu. M., 14th World Renewable Energy Congress - WREC 2015, Bucuresti, Romania, 8-12 June- oral presentation .

18. Silicon nanocomposites as dielectric elastomers. Iacob, M., Modern Science and Energy, The XXXIII-rd Edition, Cluj, 14-15 May 2015 - oral presentation.

19. Preparation of magnetic nanoparticles for biomedical applications. Iacob, M., Cazacu, M., Racles, C., Patras, X., Stiubianu, G., Tugui, C., Bele, A., Sacarescu, L., Turta, C. International Congress “Preparing the future by promoting the excellence“, The XXV-th Edition, Section B– Landmarks in modern medicine. Apollonia University, Iasi, Romania 26 February – 1 March 2015- oral presentation.

20. Discrete structures and extended networks built by flexible ligands and Zn(II) ions, Zaltariov, M., Vlad, A., Cazacu, M., Shova, S., 19-th Romanian International Conference on Chemistry and Chemical Engineering ,September 2-5 , 2015, Sibiu, Romania- oral presentation.

21. Mn(II) and Zn(II)-organic frameworks: toward new magnetic and luminescent materials, Zaltariov, M., Cazacu, M., Vlad, A., Shova, S., The 3rd CEEPN Workshop on Polymer Science, September 23-26, 2015, Iasi, Romania- oral presentation.

22. Metal complexes with ligands containing dimethylsiloxane units: self-assembling ability, Cazacu, M., Soroceanu, A., Zaltariov, M., The XVIII-th International Conference "Physical Methods in Coordination and Supramolecular Chemistry" (dedicated to the memory of professor Constantin Turta and professor Mihail Revenco), October 8 – 9, 2015, Chişinău, Moldova- oral preesentation.

23. Ferrocenylsiloxane urea: synthesis, structure and properties, Dascalu, M., Balan, M., Shova,S., Racles, C., Cazacu, M., The XVIII-th International Conference "Physical Methods in Coordination and Supramolecular Chemistry" (dedicated to the memory of professor Constantin Turta and professor Mihail Revenco), October 8 – 9, 2015, Chişinău, Moldova- oral presentation.

24. Self-Assembled Cu(II) Coordination Complexes Based on Mixed Ligands: Silicon-Containing Carboxylic Acids and N-Donor Ligand , Vlad, A., Cazacu, M., Shova, S., Zaltariov, M., - 19-th Romanian International Conference on Chemistry and Chemical Engineering September 2-5 , 2015, Sibiu, Romania-poster.

25. 2D manganese(II) networks based on V-shaped bis(p-carboxyphenyl)diphenylsilane: synthesis, structures and properties, Vlad, A., Zaltariov, M., Cazacu, M., Shova, S., The XVIII-th International Conference "Physical Methods in Coordination and Supramolecular Chemistry" (dedicated to the memory of professor Constantin Turta and professor Mihail Revenco), October 8 – 9, 2015, Chişinău, Moldova-poster.

26. Superparamagnetic iron oxide nanowires self-assembled into smectic crystal, Iacob, M., Tugui, C., Sirbu, D, Stiubianu, G., Cazacu, M., The XVIIIth International Conference "Physical Methods in Coordination and Supramolecular Chemistry". Chişinău, Moldova, October 8-9, 2015, poster.

Element

Wmass / Watoms %

SM1 SM2 SM3

Fe Wmass % 4,13 6,47 8,36

Watoms% 1,13 1,79 2,21

Cr Wmass % 11,77 11,07 2,67

Watoms% 3,45 3,30 0,76

Objective 2. Obtaining of the siloxane compounds as structural building units (SBUs). Synthesis of carboxylic acids containing siloxane or silane moieties

Some results-2013-Scientific Report 2013Objective 1. Preparation of the polynuclear transition metal μ-oxo clusters

XRD molecular structures of the μ-oxo clusters Cu-Cr (a) and Cu-Cr-Fe (b) derived from 3-furoic acid

XRD structure of [Fe3O(C4H3OCOO)6(CH3OH)3]∙NO3·H2O ,

equivalent for Fe-Cr clusters SM1, SM2 and SM3

FTIR spectrum of the siloxane-containing acid

HNMR spectrum of the siloxane-containing acid

FTIR spectrum of the silane-containing acid

HNMR spectrum of the silane-containing acid

XRD structure of the silane-containing acid

Some results-2014-Scientific Report 2014Objective 1. Obtaining of the siloxane or silane compounds as structural building units (SBUs) for metal-containing networks. Synthesis of amines and their derivatives containing siloxane or silane moieties.

Objective 2. Preparation of the extended networks containing metals by using the obtained ligands

Absorption (a) and emission(b) spectra of the Schiff base derivative

XRD structure of the diamine with silane moiety

XRD structure of the Schiff base derivative with silane moiety

XRD structure of the [Cu(HIm)4(H2O)2]2+( L2-) network based on 1,3-bis(p-carboxyphenylene-

ester-methylene)tetramethyldisiloxane

XRD structure of the [Cu(Bpy)2(HL1)]ClO4·DMF·H2O network based on bis(carboxyphenylene)diphenylsilane

Objectivul 2. Preparation of the extended networks having preformed or “in situ“ formed metal clusters and the obtained siloxane or silane ligands

Some results-2015-Scientific Report 2015Objectivul 1. Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands (continued)

SiO

OHO

OHZn(NO3)2x 6 H2O

DMF

125 oC, 72 h{[Zn2(COO)4(DMF)2]·0.8DMF}n

{[Mn6(µ3-O)2(salox)6(H2salox)(H2O)3H2L]}n

SEM and TEM images of the aggregate from chloroform

AFM images: (a) phase contarst; (b)- 2D topographic; (c) 3D topographic

TG-DTG Curves

Hexanuclear cluster Mn6(µ3-O)2

Sorption/desorption isotherms and TEM image of the coordination polymer [CuL2]n

[CuL2]n

X-ray structure of the coordination Zn(II) polymer

Dr. Maria Cazacu Prof. Constantin TurtaDr. Carmen RaclesDr. Sergiu ShovaDr. Mihaela AlexandruDr. Alexandra BarganA.C. Angelica VladDr. Mirela-Fernanda Zaltariov Dr. Alina Soroceanu Drd. Ana-Maria-Corina Dumitriu Drd. Mihail Iacob

“Petru Poni” Institute of Macromolecular Chemistry, IasiAleea Gr. Ghica Voda 41 A, 700487, IasiTel.: 0232-217454; Fax: 0232-211299

Dr. Maria Cazacu – Project DirectorE-mail: mcazacu@icmpp.ro