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 Contract No.53/ Project durationSeptember 2013-September 2016 Granted byUEFISCDI 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.

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Preparation of the polynuclear transition metal μ-oxo clusters 2.Obtaining of the siloxane or silane compounds as structural building units (SBUs) of the metal-organic networks Obtaining of the siloxane or silane compounds as structural building units (SBUs) of the metal-organic networks 2.Preparation of the extended networks containing metals by using the obtained siloxane or silane ligands 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 Preparation of the extended networks having preformed or “in situ” formed metal clusters and the obtained siloxane or silane ligands (continued) 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, 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– 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 {Dy 2 Ba(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– 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,

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, Metallopolymers based on a polyazomethine ligand containing oxadiazole rigid and tetramethyldisiloxane flexible units, Mirela-Fernanda Zaltariov, Maria Cazacu, Carmen Racles, Valentina Musteata, Angelica Vlad, Anton Airinei, J.Appl. Polym. Sci.-2014, DOI: /app.41631

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

Element W mass / W atoms % SM1SM2SM3 FeW mass %4,136,478,36 W atoms %1,131,792,21 CrW mass %11,7711,072,67 W atoms %3,453,300,76 Objective 2. Obtaining of the siloxane compounds as structural building units (SBUs). Synthesis of carboxylic acids containing siloxane or silane moieties Some results Scientific Report 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 [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]∙NO 3 · H 2 O, 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 Scientific Report 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 (H 2 O) 2 ] 2+ ( L 2- ) at different temperatures. XRD structure of the [Cu(HIm) 4 (H 2 O) 2 ] 2+ ( L 2- ) network based on 1,3-bis(p-carboxyphenylene- ester-methylene)tetramethyldisiloxane XRD structure of the [Cu(Bpy) 2 (HL 1 )]ClO 4 ·DMF·H 2 O network based on bis(carboxyphenylene)diphenylsilane

Dr. Maria Cazacu Prof. Constantin Turta Dr. Carmen Racles Dr. Sergiu Shova Dr. Mihaela Alexandru Dr. Alexandra Bargan A.C. Angelica Vlad Drd. Mirela-Fernanda Zaltariov Drd. Alina Soroceanu Drd. Ana-Maria-Corina Dumitriu Drd. Mihail Iacob 2014 Dr. Maria Cazacu Dr. Carmen Racles Dr. Sergiu Shova A.C. Angelica Vlad Drd. Mirela-Fernanda Zaltariov Drd. Alina Soroceanu Drd. Ana-Maria-Corina Dumitriu Drd. Mihail Iacob

“Petru Poni” Institute of Macromolecular Chemistry, Iasi Aleea Gr. Ghica Voda 41 A, , Iasi Tel.: ; Fax: Dr. Maria Cazacu – Project Director