1. NEW COORDINATION NETWORKS CONTAINING POLYFUNCTIONAL FLEXIBLE BRIDGES
INNOVATION AND CREATIVITY
EXECUTIVE AGENCY FOR HIGHER EDUCATION, RESEARCH, DEVELOPMENT AND INNOVATION FUNDING
NEW COORDINATION NETWORKS
CONTAINING POLYFUNCTIONAL
FLEXIBLE BRIDGES
EXPLORATORY RESEARCH PROJECTS
Contractor
"Petru Poni" Institute of Macromolecular Chemistry, Romanian Academy
Project:
PN-II-ID-PCE
Contract No.
53/
Project duration
September 2013-September 2016
Granted by
UEFISCDI
Project Director
Dr. Maria Cazacu

2. Description
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.

3. Budget Stage 2013 265.000,00 Stage 2014 263.718,00 Stage 2015
,00
Stage 2016
,00
Total Budget
, 00

4. Objectives
2013
Preparation of the polynuclear transition metal μ-oxo clusters
Obtaining of the siloxane or silane compounds as structural building units (SBUs) of the metal-organic networks
2014
Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands
2015
Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands (continued)
Preparation of the extended networks having preformed or “in situ” formed metal clusters and the obtained siloxane or silane ligands
2016
Evaluation of some properties and potential applications for the metal-silicone networks

5. Dissemination Articles
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,
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,
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.
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,
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.
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,
Articles

6. Articles
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 , 132,
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,
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,

7. Articles
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,
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,
16. Sonochemical synthesis of hematite nanoparticles, M. Iacob, Chemistry Journal of Moldova, 2015, 1,
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, ,
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: /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: /j.poly
Phd. Thesis-2014
1. Structural and morphological changes induced by the presence of the siloxane blocks in metal-organic complexes, drd. Alina Soroceanu, 24 September 2014.
2. Metal complexes, polymers and coordination networks based on siloxane and silane ligands, drd. Mirela-Fernanda Zaltariov, 29 September 2014.

8. Presentations at International Scientific Meetings-2013
1. Functionalized polyhedral oligomeric silsesquioxanes: synthesis and structural characterization; Dumitriu, A.–M.-C.; Cazacu, M.; Shova, S., 18-th Romanian International Conference on Chemistry and Chemical Engineering, Sinaia, 4-7 Septembrie 2013, Romania-oral presentation.
2. Cu(II) complexes based on a new ditiopic azomethine ligand containing trimethylsilyl groups; Zaltariov, M.-F.; Shova, S.; Cazacu, M.; Vlad, A., 18-th Romanian International Conference on Chemistry and Chemical Engineering, 4-7 Septembrie 2013, Sinaia, Romania-oral presentation
Presentations at International Scientific Meetings-2014
3. Nanostructures self-assembled through non-covalent bonding of metal complexes with ligands containing siloxane or silane fragments, Zaltariov, M. F.; Cazacu, M.; Vlad, A., The 8th International Conference on Modification, Degradation and Stabilization of Polymers, , Portoroz, Slovenia-oral presentation.
4. Coordination polymers and networks build on the basis of flexible dicarboxylate ligands and different metallic ions, Zaltariov, M. F.; Cazacu, M.; Vlad, A.; Shova, S. The 2nd CEEPN Workshop on polymer science, October 24-25, 2014, “Petru Poni” Institute of Macromolecular Chemistry, Iasi, Romania-poster.
5. Morphology and behavior of solid state metal complexes of Cu (II) with flexible ligands, Soroceanu, A.; Vlad, S.; Cazacu, M. 10th International Conference on Physics of Advanced Materials, Septembrie 2014, Iasi, Romania-poster.
6. Electrochemical and antimicrobial activity of some copper complexes of siloxane-containing ligands, Soroceanu, A.; Cazacu, M.; Vornicu, N.; Vacareanu, L. Le huitieme colloque franco-roumain de chimie appliquee, Septembrie 2014, Montpellier, Franţa-poster.
7. Functional and flexible nanostructured coordination polymers, Vlad, A.; Zaltariov, M.F.; Cazacu, M., The 8th International Conference on Modification, Degradation and Stabilization of Polymers, , Portoroz, Slovenia-poster

9. 8. Des composites polysiloxane–complexes métalliques
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 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, 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, 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, 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, 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, Mai 2014, Chisinau, Moldova-poster.

10. Presentations at International Scientific Meetings-2015
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, May 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 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.

11. 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.

12. Presentations at National Scientific Meetings-2013
1.New supramolecular polyhedral oligomeric silsesquioxanes: synthesis and structural characterization; Dumitriu, A.–M.-C.; Cazacu, M.; Shova, S., Zilele Universităţii "Alexandru Ioan Cuza” -Recent Achievements in Organic and Supramolecular Chemistry, 31 October –02 November 2013, Iasi, Romania-oral presentation.
Presentations at National Scientific Meetings-2014
2. Strategies for the preparation of iron oxide nanoparticles from carboxy-clusters, Iacob, M.; Cazacu, M.; Racles, C.; Ursu, L.; Sacarescu, L.; Turta, C., The XXXIII-rd National Conference of Chemistry Călimăneşti – Căciulata, Vâlcea, Romania, 1-3 October 2014, -oral presentation.
3. Cu(II) and Zn(II) complexes: from discrete molecules to extended networks, Zaltariov, M.F.; Cazacu, M.; Vlad, A., The XXXIII-rd National Conference of Chemistry Călimăneşti – Căciulata, Vâlcea, Romania, 1-3 October 2014 – oral presentation.
4. New trinuclear clusters with 3-furoic acid, Iacob, M.; Cuzan, O.; Cazacu, M.; Shova, S.; Turta, C., The XXXIII-rd National Conference of Chemistry Călimăneşti – Căciulata, Vâlcea, Romania, 1-3 October poster.
5. Azomethine ligands with attached silatranyl group: synthesis, structural analysis, evaluation of thermostability and the biological activity, Dumitriu, A.M.C.; Iacob, M.; Vlad, A.; Bargan, A.; Vornicu, N.; Shova, S.; Cazacu, M., The XXXIII-rd National Conference of Chemistry Călimăneşti – Căciulata, Vâlcea, Romania, 1-3 October poster.

13. Presentations at National Scientific Meetings-2015
6. Synthesis, structural characterization and magnetic properties of a polymerc complex built by hexanuclear clusters and flexible ligands, Zaltariov, M., Cazacu, M., Shova, S., Vlad, A., Iasi Academic Days-The XXV-th Session of scientific communications of „Petru Poni„ Institute of Macromolecular Chemistry Iasi, September oral presentation.
7. Metallic complexes with Schiff base ligand containing siloxane segment, Soroceanu, A., Cazacu, M., Iasi Academic Days-The XXV-th Session of scientific communications of „Petru Poni„ Institute of Macromolecular Chemistry Iasi, september oral presentation.
8. Metallic complexes of flexible Schiff bases self-assembled in supramolecular structures, Vlad, A., Cazacu, M., Shova, S., Zaltariov, M., Iasi Academic Days-The XXV-th Session of scientific communications of „Petru Poni„ Institute of Macromolecular Chemistry Iasi, 24 – 26 September poster.
9. Cu(II) and Zn(II) complexes of Schiff bases derived from trimethylsilyl-propyl-p-aminobenzoate, Zaltariov, M., Vlad, A., Cazacu, M., Shova, S., Iasi Academic Days-The XXV-th Session of scientific communications of „Petru Poni„ Institute of Macromolecular Chemistry Iasi, September poster.

14. Some results-2013-Scientific Report 2013
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 2013
Objective 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
Element
Wmass / Watoms %
SM1
SM2
SM3 Fe
Wmass %
4,13
6,47
8,36
Watoms%
1,13
1,79
2,21 Cr
11,77
11,07
2,67
3,45
3,30
0,76

15. Some results-2014-Scientific Report 2014
Objective 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
Water vapor sorption-desorption isotherms of the [Cu(HIm)4(H2O)2]2+( L2-) at different temperatures.
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

16. X-ray structure of the coordination Zn(II) polymer
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 2015
Objectivul 1. Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands (continued)
[CuL2]n
X-ray structure of the coordination Zn(II) polymer
Sorption/desorption isotherms and TEM image of the
coordination polymer [CuL2]n
AFM images: (a) phase contarst; (b)- 2D topographic; (c) 3D topographic
{[Mn6(µ3-O)2(salox)6(H2salox)(H2O)3H2L]}n
TG-DTG Curves
SEM and TEM images of the aggregate from chloroform
Hexanuclear cluster Mn6(µ3-O)2

17. Team Dr. Maria Cazacu Prof. Constantin Turta Dr. Carmen Racles
Dr. Sergiu Shova
Dr. Mihaela Alexandru
Dr. Alexandra Bargan
A.C. Angelica Vlad
Dr. Mirela-Fernanda Zaltariov
Dr. Alina Soroceanu
Drd. Ana-Maria-Corina Dumitriu
Drd. Mihail Iacob

18. Contact Dr. Maria Cazacu – Project Director E-mail: mcazacu@icmpp.ro
“Petru Poni” Institute of Macromolecular Chemistry, Iasi
Aleea Gr. Ghica Voda 41 A, , Iasi Tel.: ; Fax:
Dr. Maria Cazacu – Project Director