Transcript Slide 1

Exploratory research project,
funded by CNCSIS, program PN II ‘Idei’
Contract no. 506/14.01.2009
LUMINESCENT MOLECULAR MATERIALS OBTAINED
BY SELF-ASSEMBLY PROCESSES
Director: Dr. Gabriela MARINESCU
Lenght: 14.01.2009 – 30.11.2011
Summary
The present research proposal develops a systematic study of the synthesis and
photophysical properties of metal-supramolecular systems obtained by using each of
following luminescent species or their combination: a) complexes built with Zn(II), Cd(II)
ions (d10 electronic configuration) and Schiff base compartmental ligands, the
luminescence being generated mainly by the organic backbone; b) lanthanide(III)
containing complexes [4f luminescent ions in the visible – Tb(III), Eu(III), or near infrared
region – Pr(III), Nd(III), Er(III), Yb(III)]; c) supramolecular syntons built on metalophilic
interactions (d8- d8, d10 - d10). The major goals of the proposal are to build luminescent
crystalline metal organic networks containing three different luminescent species
(combination of d10, 4f chromophores and d8-d8, d10-d10 metalophilic interactions) and,
also, to synthesize chiral-luminescent homo- and heterometallic systems by the selfassembly of metal units with chiral organic linkers, in order to get multifunctional
systems through the combination of two properties (fluorescent and optical). The
supramolecular systems will be characterized by X-ray single-crystal diffraction, various
spectroscopic (IR, UV-VIS, NIR) and also special measurements according to their
properties (fluorescence, magnetism). The rational combination of different properties
opens the way to technical application of these systems.
Objectives
 Rational synthesis of luminescent supramolecular systems built on
homo- and heterometallic tectons (d10-d10, d10-4f, 4f-4f and 4f-4f’)
 Design of heterometallic supramolecular architectures by using two
luminescence sources (d10 or 4f luminophores and d8-d8, d10-d10
metalophilic interactions)
 Chiral-luminescent homo- and heterometallic systems by the selfassembly of metal units with chiral organic linkers
 Luminescent crystalline metal organic networks containing three
different luminescent species (combination of d10, 4f chromophores and
d8-d8, d10-d10 metalophilic interactions). This would be the first time such
a system is synthesized
 Investigation of the luminescent properties of the newly synthesized
molecular systems; magneto-structural correlations for the systems that
contain paramagnetic metal ions (especially 4f ions).
Team
Crt.
No.
Surname and first
name
Year of
birth
Didactic
/scientific title
Doctorate
1
Marinescu Gabriela
1972
Researcher
Yes
2
Gheorghe Ruxandra
Florina
1976
Lecturer
Yes
3
Visinescu Diana Beatrice
1974
Researcher
Yes
4
Madalan Augustin Madalin
1973
Lecturer
Yes
5
Branzea Diana Georgiana
1979
Researcher
Yes
6
Pasatoiu Traian Dinu
1981
PhD-student
Budget
CRT.
No.
Value 2009
(lei)
Value 2010
(lei)
Value 2011
(lei)
TOTAL
Value
(lei)
58675
105000
140000
303675
16006,2
27500
46600
90106,2
(participation in prestigious scientific events / documentation;
research stages in contry or abroad)
0
2100
15000
17100
LOGISTICS COSTS for carryng on the project
(research infrastructure, cost for materials, dissemination, etc.)
30361
40400
78400
149161
TOTAL
105042,2
175000
280000
560042,2
NAME OF THE BUDGET CATEGORY
STAFF EXPENSES
1.
2.
-
max. 60% including state tax or
other contribution
INDIRECT EXPENSES (overheads)
MOBILITIES
3
4.
5.
Curriculum Vitae Gabriela Marinescu
Education: 1991 - High School on Chemistry, Bucharest, 1996 - B.Sc Inorganic Chemistry, Faculty of Chemistry, University of Bucharesti; 1997 –
M.Sc Coordination Chemistry, Faculty of Chemistry, University of Bucharest; 2003 – Ph.D Chemsitry, Faculty of Chemistry, University of Bucharest;
Topic of thesis: "Polymetallic Supramolecular Architectures Based on Oxalato-Bridges", Advisor: Acad. Marius Andruh.
Since 1997 till now - researcher at the Institute of Physical Chemistry “Ilie Murgulescu”, Laboratory of Coordination and Supramolecular Chemistry; since
2004 - Lecturer at the Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest.
Scientific fields of interest:
Coordination Chemistry; Supramolecular Chemistry; Molecular Magnetism.
- polynuclear coordination compounds chemistry. Synthesis strategies (building block) of homo- and heteropolynuclear coordination compounds (selfassembly in polimetallic systems); - synthesis of polidentate ligands and use of them in polymetallic architectures design;
- metallosupramolecular chemistry – polymetallic supramolecular architectures through the interplay of coordinative bonds with other non-covalent
interactions (hydrogen bonds, - stacking, metallophilic interactions); - study of magnetic properties of the polynuclear coordination compounds,
magneto-structural correlations; - physico-chemical characterisation of newly synthesized componds by IR, UV-Vis, NIR spectroscopy, magnetic
measurements; - growth of single crystals by various techniques (slow evaporation, slow diffusion, hydrothermal and solvothermal synthesis); epitaxial
growth of monocrystalline layers of an isomorphous monocrystal (crystals of crystals);
- processing of the magnetic and crystalographic data using suitable programs (Kaleidagraph, Origin, Diamond, XP). - synthesis of polynuclear
coordination compounds – precursors for materials with special properties (mixed oxides and complex sulphides generators compounds). Design and
synthesis of nanomaterials (mono- and polymetallic) with special magnetic properties.
Reprezentative papers:
1. R. Lescouezec, G. Marinescu, J. Vaisermann, F. Lloret, J. Faus, M. Julve, M. Andruh, Inorg. Chim. Acta 2003, 350, 131-142.
2. G. Marinescu, D. Visinescu, A. Cucos, M. Andruh, Y. Journaux, V. Kravtsov, Y. A. Simonov, J. Lipkowski, Eur. J. Inorg. Chem. 2004,
2914-2922.
3. G. Marinescu, C. Ovezea, N. Avarvari, M. Andruh, Rev. Roum. Chim. 2004, 49, 221-226.
4. L. Patron, I. Mindru, G. Marinescu, Encyclopedia of Nanoscience and Nanotechnology”, Marcel Dekker, New York, 2004, 1683-1699.
5. G. Marinescu, M. Andruh, M. Julve, F. Lloret, R. Llusar, S. Uriel, J. Vaissermann, Cryst. Growth & Design 2005, 5, 261-267.
6. G. Marinescu, L. Patron, Daniela C. Culita, C. Neagoe, C. I. Lepadatu, I. Balint, L. Bessais and C. Bazil Cizmas, Journal of Nanoparticle
Research, 2006, 8(6), 1045-1052.
7. G. Marinescu, S. Ferlay, N. Kyritsakas, M. W. Hosseini, Dalton Trans 2008, 615.
8. D. C. Culita, G. Marinescu, L. Patron, O. Carp, C. B. Cizmas, L. Diamandescu, Materials Chemistry and Physics 2008, 111, 381-385.
9. D.C. Culita, G. Marinescu, L. Patron, L. Diamandescu, Rev. Roum. Chim. 2010, 55(2), 131-135.
10. D.C. Culita G. Marinescu, L Patron, F. Tuna, N. Stanica, Ma Yun, Rev. Roum. Chim. 2010, 55(1), 63-67.
11. G. Marinescu, G. Marin, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, Cryst. Growth & Design 2010, 10, 2096-2103.
12. G. Marinescu, M. Andruh, F. Lloret, M. Julve, Coord. Chem. Rev. 2010, accepted.
Curriculum Vitae Ruxandra Florina Gheorghe
Education: B.Sc. Inorganic Chemistry (1999), M.Sc. Coordination Chemistry (2001), Ph.D. Chemistry (2005) (Thesis title 3d-4f
Supramolecular Polymetallic Architectures, advisor Prof. Dr. Marius Andruh), Faculty of Chemistry, University of Bucharest.
Teaching assistant (2002-2004); assistant professor (2004-2009); Lecturer (2009) at the Inorganic Chemistry Laboratory, Faculty of
Chemistry, University of Bucharest.
Scientific fields of interest:
synthesis of polymetallic complexes; molecular magnetism; supramolecular magnetism.
- rational synthesis of 3d-3d, 3d-3d’, 3d-4f supramolecular polymetallic systems with different nuclearities and dimensionalities; - rational
synthesis of 3d-3d’-4f heterotrimetallic systems containing three different paramagnetic metal ions; - enantioselective synthesis of chiral
molecular magnets; - synthesis of organic ligands; - investigation of structural, magnetic and optic properties of the resulting complexes;
- technical skills: spectroscopic measurements (IR, NIR, UV-Vis, 1H-NMR, circular dichroism), polarimetry, SQUID magnetic measurements;
-study of magnetic data using the Kaleidagraph and Origin programs, and of crystallographic data using the XP, Diamond and Mercury
programs.
Main journal publications:
1. J.-P. Costes, R. Gheorghe, M. Andruh, S. Shova, J.-M. Clemente Juan, New Journal of Chemistry 2006, 30, 572 – 576 (Ed. Royal Society
of Chemistry).
2. C. Train, K. Boubekeur, M. Gruselle, M. Verdaguer, R. Gheorghe, N. Ovanesyan, European White Book on Molecular Magnetism (NMP3CT-2005-515767) – FP6, MAGMANet NoE, 2006, 106-107.
3. R Gheorghe, M. Andruh, J.-P. Costes, B. Donnadieu, M. Schmidtmann, A. Müller, Inorganica Chimica Acta 2007, 360, 4044-4050 (Ed.
Elsevier).
4. R. Gheorghe, L.-M. Chamoreau, N.S. Ovanesyan, S.M. Aldoshin, J. Kapitan, L. Hecht, L. D. Barron, C. Train, M. Gruselle, Chirality 2008,
20, 1085-1091 (Ed. Wiley-VCH).
5. C. Train, R. Gheorghe, V. Krstic, L.-M. Chamoreau, N.S. Ovanesyan, G.L.J.A. Rikken, M. Gruselle, M. Verdaguer, Nature Materials 2008,
7, 729-734 (Ed. Nature Publishing Group
6. J.P. Costes, B. Donnadieu, R. Gheorghe, G. Novitchi, J.P. Tuchagues, L. Vendier, Eur. J. Inorg. Chem. 2008, 33, 5235-5244 (Ed. WileyVCH).
7. A. Sukhanov,R. Galeev, L. Mingalieva, V. Voronkova, R. Gheorghe, M.Andruh, Appl. Magn. Res. 2009, 35, 613-623 (Ed. Springer Wien
New York).
8. M. Andruh, D.G. Brânzea, R. Gheorghe, A.M. Mădălan, Cryst. Eng. Comm. 2009, 11, 2571-2584 (Ed. Royal Society of Chemistry).
9. R. Gheorghe, A.M. Madalan, J.P. Costes, W. Wernsdorfer, M. Andruh, Dalton Trans., 2010, 39, 4734-4736
.
Curriculum Vitae Diana Beatrice Visinescu
Educations: B.Sc. in Chemistry (1997) and of M. Sc. in Chemistry -specialization: Coordination Chemistry (1998) at the Faculty of
Chemistry, University of Bucharest. In 2003 she has been rewarded with the title of Ph. D. in Chemistry by the same University. From
2002 she is employed as a researcher by the Coordination Chemistry Laboratory, Institute of Physical Chemistry Ilie Murgulescu,
Bucharest.
RESEARCH INTERESTS:
Rational synthesis of pollymetallic complexes; molecular magnetism; supramolecular chemistry.
-the search and developement of new synthetic routes of oligonuclear complex systems with interesting stuctural features; -self-assembly
of molecular building-block units in order to obtain heterotrimetallic systems with three different spin carriers; -optical and magnetostructural characterization; interpreting the experimental data; - magnetic and crystalographic data interpretation using appropriate
software (Kaleidagraph, Origin, XP, Diamond, Mercury).
Reprezentative papers:
1. G. Marinescu, D. Visinescu, A. Cucos, M. Andruh, Y. Journaux, V. Kravtsov, Y. A. Simonov, J. Lipkowski, Eur. J. Inorg. Chem. 2004,
2914-2922.
2. D. Visinescu, J.-Pascal Sutter, H. W. Roesky, J. Magull, M. Andruh, Rev. Roum. Chim., 2005, 50(9-10).
3. D. Visinescu, J.-Pascal Sutter, C. Ruiz Perez, M. Andruh, Inorg. Chim. Acta, 2006, 359, 433-440.
4. D. Visinescu, C. Desplanches, I. Imaz, V. Bahers, R. Pradhan, F. A. Villamena, P. Guionneau, J. Pascal Sutter, J. Am. Chem. Soc.,
2006, 128, 10202.
5. D. Visinescu, L. M. Toma, F. Lloret, O. Fabelo, C. Ruiz-Pérez and M. Julve, Dalton Trans., 2008, 4,103-4105.
6. D. Visinescu, L. M. Toma, O.Fabelo, C. Ruiz-Pérez, F. Lloret, M. Julve, Polyhedron 2009, 28, 851-859.
7. D. Visinescu, L. M. Toma, F. Lloret, O. Fabelo, C. Ruiz-Pérez and M. Julve, Dalton Trans. 2009, 37-40.
8. D. Visinescu, A. M. Madalan, M. Andruh, C. Duhayon, J.-P.Sutter, L. Ungur, W. Van den Heuvel, L.F. Chibotaru, Chem. Eur. J. 2009,
11808-11814.
9. D. Visinescu, L. Marilena Toma, J. Cano, O. Fabelo, C.R.-Pérez, A.Labrador, F. Lloret, M. Julve, Dalton Trans., 2010, 39, 5028-5038.
10. D. Visinescu, O. Fabelo, C.R. Pérez, F. Lloret, M. Julve, CrystEngComm 2010, in press.
Curriculum Vitae Augustin Madalin Madalan
Education: 1998 - UMF „Carol Davila”, Faculty of Medicine; B.Sc. Inorganic Chemistry (2000), Ph.D. Chemistry (2004) Faculty of
Chemistry, University of Bucharest advisor Prof. Dr. Marius Andruh
-
2004 assistant professorat the Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest.
Lecturer (2008) at the Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest.
Scientific fields of interest:
Coordination Chemistry; Supramolecular Chemistry; Metal Chemistry; Stereochemistry of the Coordination Compounds; Molecular
Magnetism; Inorganic Biomolecule; Inorganic Compounds with Therapeutic Activity.
Main journal publications:
1.
2.
3.
4.
5.
6.
7.
8.
G. Marin, M. Andruh, A. M. Madalan, A. J. Blake, C. Wilson, N. R. Champness, M.Schröder, Cryst. Growth & Design, 2008, 8, 964975.
A. M. Madalan, N. Avarvari, M. Fourmigué, R. Clérac, L. F. Chibotaru, S. Clima, M. Andruh, Inorg. Chem., 2008, 47, 940-950.
C. Ene, A. M. Madalan, C. Maxim, B. Jurca, N. Avarvari, M. Andruh, J.A.C.S., 2009, 131, 4586-4587.
D. G. Branzea, R. Gheorghe, A. M. Madalan, M. Andruh, Cryst. Eng. Comm., 2009, 11, 2571-2584.
D. Visinescu, A. M. Madalan, M. Andruh, C. Duhayon, J.-P. Sutter, L. Ungur, W. Van den Heuvel, L. F. Chibotaru, Chem. Eur. J.,
2009, 15, 11808- 11814.
A. M. Madalan, C. Réthoré, M. Fourmigué, E. Canadell, E. B. Lopes, M. Almeida, P. Auban-Senzier, N. Avarvari, Chem. Eur. J.,
2010, 16, 528-537.
V. Tudor, A. Madalan, V. Lupu, F. Lloret,M. Julve, M. Andruh, Inorg. Chim. Acta, 2010, in press.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, Inorg. Chem. 2010, 49, 2310-2315.
.
9.
R. Gheorghe, A.M. Madalan, J.P. Costes, W. Wernsdorfer, M. Andruh, Dalton Trans., 2010, 39, 4734-4736
10. T.D. Pasatoiu, M. Etienne, A.M. Madalan, M. Andruh, R. Sessoli, Dalton Trans., 2010, 39, 4802-4808.
11. G. Marinescu, G. Marin, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, Cryst. Growth & Design 2010, 10, 2096-2103.
Curriculum Vitae Diana Georgiana Branzea
Education: 2002 - B.Sc. Inorganic Chemistry, 2004 - M.Sc. Coordination Chemistry, 2004 – present Ph.D student (Chemistry) Faculty of
Chemistry, University of Bucharest, under the supervisinon of Prof. Marius Andruh; In november 2004, after passing the admission
exam organized by the Faculty of Chemistry, University of Bucharest, she was admitted as a Ph.D student with the title of the thesis:
Supramolecular polymetallic systems obtained using the anionic complex [Cu(mal)2]2- under the supervision of Prof. Marius Andruh.
Relevant work experince:
-synthetic strategies (node and spacer, building block) of homo- and heteropolynuclear complexes of controlled dimensionality (the
chemistry of polynuclear complexes); -synthesis of polydentate ligands (organic chemistry) and rational use of such ligands in
designing polymetallic systems; -supramolecular polimetallic systems using a variety of supramolecular interactions – hydrogen
bonds, π-π stacking interactions, metallophilic interactions (supramolecular chemistry); -experimental techiniques of investigation
structural (X-ray diffraction, IR, UV-Vis and NIR spectroscopy) and magnetic properties of the synhesized complexes (criomagnetic
measurements); -transforming the experimental data into physical information using specific software –Shelxl, Kaleidagraph, Origin,
Diamond, XP and interpretation of resulting data.
Papers:
1. Heterobinuclear Complexes as Tectons in Designing Coordination Polymers, D. G. Branzea, A. Guerri, O. Fabelo, C. Ruiz-Perez, L. M.
Chamoreau, C. Sangregorio, A. Caneschi, M. Andruh, Cryst. Growth & Design 2008, 8, 941-949.
2. Conducting mixed-valence salt of bis(ethylenedithio)tetrathiafulvalene BEDT-TTF) with the paramagnetic heteroleptic anion
[CrIII(oxalate)2(2,2’-bipyridine)]-, A. M. Madalan, E. Canadell, P. Auban-Senzier, D. Branzea, N. Avarvari, M. Andruh, New J. Chem.,
2008, 32, 333–339.
3. A 2D Coordination Polymer with Canted ferromagnetism Constructed from Ferromagnetic [NiIICoII] Nodes, D.G. Branzea, L. Sorace,
C. Maxim, M. Andruh, A. caneschi, Inorg. Chem. 2008, 47, 6590-6592.
4. D. G. Branzea, R. Gheorghe, A. M. Madalan, M. Andruh, Cryst. Eng. Comm., 2009, 11, 2571-2584.
Curriculum Vitae Traian Dinu Pasatoiu
Education: 2000 - Al. D. Ghica Highscoool, Alexandria; 2004 – Bachelor Degree in Chemistry - The Faculty of Chemistry, University of
Bucharest; 2006 – Master Degree in Coordination Chemistry - The Faculty of Chemistry, University of Bucharest; 2006 – present:
PhD student in Coordination Chemistry at the Doctoral School in Chemistry, University of Bucharest; Following the admission
examination from October 2006, I become a PhD student at the University of Bucharest, under the scientific supervision of Prof. Dr.
Marius Andruh, the subject of my PhD thesis being Heteropolynuclear complex combinations that contain 3 different spin carriers: 3d4f-4d or 3d-4f-5d.
Skills: coordination chemistry; supramolecular chemistry; magnetism:
- rational synthesis of polynuclear complexes using various reaction approaches; - syntesis of organic ligands; - investigatation of
the structure and optical properties of the synthesized compounds, using UV-VIS, NIR and IR spectroscopy and X-Ray structure
determinations; - analysis and explanation of the magnetic and crystalografic results using the appropiate computer software
(Kaleidagraph, Origin, Diamond, XP, Mercury).
Papers:
1.
2.
3.
4.
C. Maxim, T. D. Pasatoiu, V. Ch. Kravtsov, S. Shova, C. A. Muryn, R. E. P. Winpenny, F. Tuna, M. Andruh, Copper(II) and zinc(II)
complexes with Schiff-base ligands derived from salicylaldehyde and 3-metoxysalicylaldehide: synthesis, crystal structures, magnetic
and luminescence properties, Inorg. Chim. Acta. 2008, 361, 3903-3911.
Cu(II) Complexes imobilized on Functionalized Mesoporous Silica as Catalysts for biomimetic oxidations, M. Muresan, V. Parvulescu,
R. Ene, M. Cioatera, T.D. Pasatoiu, M. Andruh, J. Mater. Sci. iunie 2009
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, Inorg. Chem. 2010, 49, 2310-2315.
T.D. Pasatoiu, M. Etienne, A.M. Madalan, M. Andruh, R. Sessoli, Dalton Trans., 2010, 39, 4802-4808.
Results
G, Marinescu, G, Marin, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, “New molecular rectangles and
coordination polymers constructed from binuclear phenoxo-bridged [Cu2] and [Zn2] tectons”, Crystal
Growth & Design. 2010, 10, 2096-2103.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke C. Tiseanu, M. Andruh, “Temperature switching of LMCT role:
From quenching to sensitivation of europium emission in a ZnII-EuIII Binuclear Complex”, Inorg. Chem.
2010, 49, 2310-2315.
G. Marinescu, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, New coordination polymers constructed
from binuclear phenoxo-bridged [Zn2] tectons, The 14th International Conference of Physical
Chemistry, ROMPHYSCHEM 14, June 2-4 2010, Bucharest, Romania.
T.D. Pasatoiu, A.M. Madalan, C. Tiseanub, M. Andruh, First SmIII Complex Exhibiting Two-Photon Induced
Fluorescent Emission, 7th International Conference of the Chemical Societies of the South-Eastern
European Countries on “Chemistry – Beauty and Application”, September 15-17 2010, Bucharest,
Romania.
G. Marinescu, A.M. Madalan, M. Andruh, C. Tiseanu, Structures and photophysical properties of d10-metal
coordination polymers based on the Schiff –base ligands, 7th International Conference of the Chemical
Societies of the South-Eastern European Countries on “Chemistry – Beauty and Application”,
September 15-17 2010, Bucharest, Romania.
G. Marinescu, A.M. Madalan, M. Andruh, C. Tiseanu, “New d10 heterometallic coordination polymers based
on compartmental Schiff-base ligands. Synthesis, structure and luminescence”, submited to Polyhedron,
2010.
T.D. Pasatoiu, A.M. Madalan, M. Andruh, C. Tiseanu, “Heterodinuclear Complexes withy NLO Properties“,
A XXXI-a Conferinta Nationala de Chimie 6-8 octombrie 2010, Ramnicu Valcea, Romania.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, “Fluorescent Emission of Europium in
Heterodinuclear ZnII-EuIII Complex, through Direct Excitation in the Visible Range“, A XXXI-a Conferinta
Nationala de Chimie 6-8 octombrie 2010, Ramnicu Valcea, Romania.
R. Gheorghe, C. Tiseanu, M. Andruh, “Study of the Luminiscent Properties of Homobinuclear 4f-4f
Complexes”, submited to Journal of Luminescence, 2010.