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 self-assembly 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 self-assembly 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 3 Visinescu Diana Beatrice 1974 4 Paraschiv Carmen Alina 1977 5 Branzea Diana Georgiana 1979 PhD-student 6 Pasatoiu Traian Dinu 1981

Budget CRT. No. NAME OF THE BUDGET CATEGORY Value 2009 (lei) Value 2010 Value 2011 TOTAL Value 1. STAFF EXPENSES - max. 60% including state tax or other contribution 58675 301325 140000 500000 2. INDIRECT EXPENSES (overheads) 16006,2 77293,8 46600 139900 3 MOBILITIES (participation in prestigious scientific events / documentation; research stages in contry or abroad) 40000 15000 55000 4. LOGISTICS COSTS for carryng on the project (research infrastructure, cost for materials, dissemination, etc.) 30361 196339 78400 305100 5. 105042,2 614957,8 280000 1000000

Curriculum Vitae Gabriela Marinescu Education: 1991 - High School on Chemistry, Bucharest, Romania, Qualification: Chemist/Assistant; 1996 - B.Sc , Faculty of Chemistry, University of Bucharesti; 1997 – M.Sc, Faculty of Chemistry, University of Bucharest; 2003 – Ph.D, Faculty of Chemistry, University of Bucharest; Inorganic Chemistry Department, Bucharest, Romania, Topic of thesis: "Polymetallic Supramolecular Architectures Based on Oxalato-Bridges", Advisor: Acad. Marius Andruh. Since 1997 till now she is working in 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. Main areas of research interests and laboratory experience: Coordination Chemistry; Supramolecular Chemistry; Molecular Magnetism. - polynuclear coordination compounds chemistry. Synthesis strategies (building block) of homo- and heteropolynuclear coordination compounds (self-assembly 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); - thermochromism and solid state reactions of some coordination compounds; - 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, C.B. Cizmas, L. Diamandescu, Rev. Roum. Chim. Accepted. 10. D.C. Culita G. Marinescu, L Patron, F. Tuna, N. Stanica, Ma Yun, Rev. Roum. Chim. Accepted.

Curriculum Vitae Ruxandra Florina Gheorghe Studii: 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 (NMP3- CT-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. Wiley-VCH). 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, in press (Ed. Royal Society of Chemistry).

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 magneto-structural 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, acceptat spre publicare.

Curriculum Vitae Carmen Alina Paraschiv Education: June 2000 - B.Sc., Department of Chemistry, University of Bucharest; June 2002 - M.Sc., Department of Chemistry, University of Bucharest; January 2006 - Ph.D., Department of Chemistry, University of Bucharest. Ph.D. Thesis: Supramolecular polynuclear systems containing the cyano group, Supervisor: Professor Marius Andruh, Corresponding Member of the Romanian Academy. 2007 – researcher, Institute of Physical Chemistry Ilie Murgulescu, Bucharest, Coordination and Supramolecular Chemistry Laboratory; 2007-present - researcer, Institutul National de Cercetare - Dezvoltare pentru Inginerie Electrica ICPE-CA, Bucuresti Competence areas: coordination chemistry; supramolecular chemistry; molecular magnetism - synthesis of low and high-dimensional polynuclear complexes; magneto-structural correlations; - design of polymetallic systems by controlling the coordination bonds and different intermolecular interactions (hydrogen bonds, aurophilic/ argentophilic interactions, - stacking interactions, etc.); - thermocromism and solid-state reactions of coordination compounds; - synthesis of polydentate organic ligands; - the study of polymetallic systems by: IR, Uv-Vis, NIR, RMN spectroscopies, magnetic measurements on SQUID magnetometer; - mass spectrometry, thermal analysis, electronic microscopy – interpreting the experimental data; - magnetic and crystalographic data interpretation using appropriate software (Kaleidagraph, Origin, XP, Diamond, Mercury). Papers: 1. B. Jurca, C. Paraschiv, A. Ianculescu, O. Carp, Journal of Thermal Analysis and Calorimetry 2009, accepted 2. F Papa, L. Patron, O. Carp, C. Paraschiv, B. Ioan, Journal of Molecular Catalysis A: Chemical 2009, 299 (1-2), pp. 93-97 3. C. Paraschiv, B. Jurca, A. Ianculescu, O. Carp, Journal of Thermal Analysis and Calorimetry 2008, 94 (2), pp. 411-416. 4. C. Paraschiv, S. Ferlay, M. W. Hosseini, N. Kyritsakas, J.-M. Planeix, M. Andruh, Rev. Roumaine Chim., 2007, 101-104. 5. C. Paraschiv, M. Andruh, Y. Journaux, Z. Zak, N. Kyritsakas, L. Ricard, J. Mater. Chem., 2006, 16, 2660- 2668. 6. C. Paraschiv, M. Andruh, S. Ferlay, M. W. Hosseini, N. Kyritsakas, J.-M. Planeix, N. Stanica, Dalton Trans., 2005, 1195-1202. 7. C. Paraschiv, S. Ferlay, M. W. Hosseini, V. Bulach, J.-M. Planeix, Chem. Commun., 2004, 2270-2271. 8. C. Paraschiv, J.-P. Sutter, M. Andruh, Inorg. Chim. Acta, 2003, 351, 385-388.

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.

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: 3d-4f-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. 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. 2. 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

Rezults Gabriela Marinescu, Geanina Marin, Augustin M. Madalan, Alis Vezeanu, Marius Andruh, “New molecular rectangles and coordination polymers constructed from binuclear phenoxo-bridged [Cu2] and [Zn2] tectons”, submitted to Crystal Growth & Design.