Transcript Document

EXECUTIVE AGENCY FOR
HIGHER EDUCATION,
RESEARCH, DEVELOPMENT
AND INNOVATION FUNDING
INNOVATION AND CREATIVITY
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
Stage 2014
Stage 2015
Stage 2016
Total Budget
265.000,00
263.718,00
522.000,00
74.282,00
1.125.000, 00
2013
1. 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
2014
1. 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
2015
1. 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
2016
1. 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, 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 1phenylethanol, 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. BadíaRomano, 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, Mirela-Fernanda Zaltariov, Maria Cazacu, Carmen
Racles, Valentina Musteata, Angelica Vlad, Anton Airinei, J.Appl. Polym. Sci.-2014,
DOI: 10.1002/app.41631
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.
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
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, 31.0804.09.2014, 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, 22-28 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 francoroumain de chimie appliquee, 15-18 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, 31.08-04.09.2014, Portoroz, Slovenia-poster
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.
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 octombrie –02
noiembrie 2013, Iasi, Romania-oral presentation.
2. Strategies for the preparation of iron oxide nanoparticles from carboxy-clusters, Iacob, M.;
Cazacu, M.; Racles, C.; Ursu, L.; Sacarescu, L.; Turta, C., A XXXIII-a Conferinţă Naţională de
Chimie Călimăneşti – Căciulata, Vâlcea, România, 1-3 Octombrie 2014, -oral presentation.
3. Cu(II) and Zn(II) complexes: from discrete molecules to extended networks, Zaltariov, M.F.;
Cazacu, M.; Vlad, A., A XXXIII-a Conferinţă Naţională de Chimie Călimăneşti – Căciulata,
Vâlcea, România, 1-3 Octombrie 2014 – oral presentation.
4. New trinuclear clusters with 3-furoic acid, Iacob, M.; Cuzan, O.; Cazacu, M.; Shova, S.;
Turta, C., A XXXIII-a Conferinţă Naţională de Chimie Călimăneşti – Căciulata, Vâlcea, România,
1-3 Octombrie 2014 -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., A XXXIII-a Conferinţă Naţională de Chimie Călimăneşti –
Căciulata, Vâlcea, România, 1-3 Octombrie 2014 -poster.
Some results-2013-Scientific Report 2013
Objective 1. Preparation of the polynuclear transition metal μ-oxo clusters
Element
Wmass / Watoms %
Fe
Wmass %
Watoms%
Cr
Wmass %
Watoms%
XRD molecular structures of the μ-oxo clusters Cu-Cr
(a) and Cu-Cr-Fe (b) derived from 3-furoic acid
SM1
SM2
SM3
4,13
1,13
11,77
3,45
6,47
1,79
11,07
3,30
8,36
2,21
2,67
0,76
XRD structure of [Fe3O(C4H3OCOO)6(CH3OH)3]∙NO3·H2O ,
equivalent for Fe-Cr clusters SM1, SM2 and SM3
Objective 2. Obtaining of the siloxane compounds as structural building units (SBUs). Synthesis of
carboxylic acids containing siloxane or silane moieties
HNMR spectrum of the siloxane-containing acid
FTIR spectrum of the
siloxane-containing acid
HNMR spectrum of the silane-containing acid
XRD structure of the silane-containing acid
FTIR spectrum of the silane-containing acid
Some results-2014-Scientific Report 2014
Objective 1. Obtaining of the siloxane or silane compounds as structural building units (SBUs) for metalcontaining networks. Synthesis of amines and their derivatives containing siloxane or silane moieties.
XRD structure of the diamine with
silane moiety
XRD structure of the Schiff base
derivative with silane moiety
Absorption (a) and emission(b) spectra of
the Schiff base derivative
Objective 2. Preparation of the extended networks containing metals by using the obtained ligands
XRD structure of the [Cu(HIm)4(H2O)2]2+( L2-)
network based on 1,3-bis(p-carboxyphenyleneester-methylene)tetramethyldisiloxane
Water vapor sorption-desorption isotherms
of the [Cu(HIm)4(H2O)2]2+( L2-) at different
temperatures.
XRD structure of the [Cu(Bpy)2(HL1)]ClO4·DMF·H2O
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, 700487, Iasi
Tel.: 0232-217454; Fax: 0232-211299
Dr. Maria Cazacu – Project Director
E-mail: [email protected]