1. REASERCH PROJECTS for YOUNG RESEARCH TEAMS Molecular and Supramolecular Heterotrimetallic Systems: towards a new generation of molecular magnetic materials PN-II-RU-TE-2011-3-0126 Project Leader: Dr. Diana VISINESCU 5.10.2011-5.10.2014

2. ABSTRACT The present project focuses on designing heterotrimetallic magnetic materials with enhanced characteristics. A special emphasis is devoted to initiating, developing and/or combining new physical properties within the heterometallic systems enclosing cores of three different spin-carriers. The rational inclusion of 3d and/or 4f cations within the same molecular entity could generate new categories of heterotrimetallic complexes: photomagnets, luminescent or chiral compounds or with combined properties, namely magneto-luminescence or magneto-chirality. These new molecular materials open large perspectives in the developing of molecular “prototypes” for revolutionary optical, high- storage devices or in quantum computing. An important part of the project is related with the human resources, both senior researchers and young graduated or Ph.D. students being employed in this project. The research theme is very actual and reliable and the obtained results will be reported in national and international ISI rated publications.

3. The main objective is the obtaining of polynuclear structures incorporating three different metal ions with enhanced magneto-optical properties (Scheme 1). Objectives Scheme 1 Specific objectives: Design and synthesis of heterotrimetallic nanomagnets Construction of 2D and 3D heterotrimetallic coordination polymers in order to generate classical molecule-based magnets with high critical temperatures. Synthesis of novel (multi)functional heterotrimetallic molecular materials: photomagnetic complexes, photo-switchable nanomagnets or with combined properties, namely magneto- luminiscent or magneto-chiral systems.

4. RESEARCH TEAM 4. Dr. Augustin Madalin MADALAN Senior Researcher (lecturer), University of Bucharest *The post-doc researcher, Ph.D. and Master student follow(-ed) post-doc/Ph.D./Master programs of the University of Bucharest. His/her experience in the synthesis, crystallization and characterization of the heterobi- and trimetallic complexes is very important in accomplishing the objectives of the research project. Dr. Diana-Beatrice VISINESCU, Senior Researcher III Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy Project leader: Research team members: 1. Dr. Maria-Gabriela ALEXANDRU post-doc researcher, University of Bucharest * 2. Dr. Traian-Dinu PASATOIU2011-2012 – Ph.D. student, University of Bucharest * 2013- Senior Researcher III, University of Bucharest 3. Dr. Gabriela MARINESCU Senior Researcher III, Institute of Physical Chemistry “Ilie Murgulescu” Romanian Academy 5. Dr. Bogdan Ciprian JURCA Senior Researcher (lecturer), University of Bucharest Andrei Alunel PATRASCU – M. Sci. student, University of Bucharest * New research team members (from 1.06.2013): Maria COCIS - technician, Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy 6. Alina Simona DINCA – Ph. D. student, University of Bucharest*

5. National and International Collaborations Acad. Marius ANDRUH University of Bucharest, Faculty of Chemistry Institute of Macromolecular Chemistry “Petru Poni”, Iasi Academia Romana Dr. Sergiu SHOVA Instituto de Ciencia Molecular (ICMol) Universitat de València SPANIA Prof. Miguel JULVE Dr. Jean-Pascal SUTTER Laboratoire de Chimie de Coordination, CNRS, Université de Toulouse, FRANTA Institut de Chimie de la Matiere Condensee (ICMCB)/Centre de Recherche Paul Pascal - CNRS, Université de Bordeaux, FRANTA Dr. Rodolphe Clérac Dr. Corinne Mathonière

6. FTIR SPECTROMETER JASCO -4100 400-4000 cm -1 Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy UV-Vis SPECTROMETER PERKIN-ELMER LAMBDA L35, 200-1100 nm JASCO FP-8300 SPECTROFLUORIMETER 200-650 nm INCUBATOR Memmert UNB500 MAIN RESEARCH FACILITIES

7. University of Bucharest, Faculty of Chemistry MAIN RESEARCH FACILITIES X-ray diffractometer on single-crystals STOE IPDS II Cryogenic SQUID magnetometer

8. Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU Dr. Gabriela MARINESCU Drd. Traian Dinu PASATOIU Drd. Alina Simona DINCA Design of heterometallic complexes exhbiting SMM or SCM properties 2011-2012 Synthesis, crystallization and characterization of precursors 3d-3d’ or 3d-4f heterometallic complexes Polycyanometallates Oxalatometallates LEWIS ACIDS LEWIS BASIS

9. Synthesis, cristallization and preliminary characterization of heterotrimetallic complexes 2011-2012 3d-4f-3(4,5)d Heterotrimetallic systems Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU Drd. Traian Dinu PASATOIU

10. 2011-2012 Structural characterization of the obtained compounds Single-crystal X-ray diffraction Dr. Augustin Madalin MADALAN University of Bucharest H 2 valpn 1-D 0-D [M’(CN) 8 ] 3- (M = Mo, W) [W(bipy)(CN) 6 ] - M II = Cu; Ln III = La, Ce, Eu, Gd, Tb, Dy, Ho M V = Mo, W M II = Cu; Ln III = Gd, Tb, Ho

11. 2011-2012 H 2 valdp 0-D 1-D H 2 valen 1-D M II = Cu; Ln III =La, Eu, Sm, Nd, Gd, Tb, Dy; M V = Mo, W [M’(CN) 8 ] 3- (M = Mo, W) {Cu II Tb III W V } M II = Cu; Ln III = Gd, Tb, Dy; M V = Mo; Ln III = La, Gd, Tb, Dy; M V = W M II = Cu; Ln III = La, Pr; M V = Mo Structural characterization of the obtained compounds

12. 2011-2012The analysis of the magnetic properties of the obtained compounds Dr. Rodolphe Clérac Dr. Corine Mathonière SCM  = 1  10 -9 s U eff = 53.9K {Cu II Tb III Mo V } SMM

13. Powder X-ray diffraction: 2011-2012Structural characterization of the obtained compounds Dr. Bogdan Ciprian JURCA University of Bucharest Chain:trinuclear 1:8

14. 2011-2012Magnetic properties Dr. Jean-Pascal SUTTER {Cu II Tb III Mo V } {Cu II Tb III W V } H DC = 3000 Oe Prof. Miguel JULVE Prof. Francesc LLORET

15. Internal and abroad short research stages 14-30 june 2012: a short research stage at Laboratoire de Chimie de Coordination (LCC) CNRS, Université Paul Sabatier, Toulouse, France – Dr. Jean-Pascal Sutter AC and DC magnetic measurements for heterotrimetallic compounds Project for one publication, preparing of manuscript Diana Visinescu Diana Visinescu, Maria-Gabriela Alexandru and Alina Simona Dinca 25-27 july 2012: a research visit at Institute of Macromolecular Chemistry “Petru Poni”, Romanian Academy, Iasi – Dr. Sergiu Shova Special X-ray diffraction measurements on single-crystals Diana Visinescu 3-30 september and 12-30 november 2012: short research stages at Instituto de Ciencia Molecular (ICMol), Universitat de Valencia– Prof. Miguel Julve Synthesis of new heteroleptic 3(4,5)d cyano-based metalloligands. Testing the reactivity of the new obtained metallocyanates against cationic complexes. Synthesis of new heterotrimetallic complexes by using the new metallocyanate ligands. Structural and DC/AC magnetic measurements of the obtained precursors and compounds. Preparing of manuscripts.

16. RESULTS 2011-2012 National and International Conferences V th International Conference on Molecular Materials. MOLMAT 2012 – Barcelona, 3-6 july 2012 1. Two structural types in one synthesis: the simultaneous formation of trinuclear and one-dimensional structures of 3d-4f-5d heterotrimetallic complexes, autori: Diana Visinescu, Maria-Gabriela Alexandru, Bogdan Jurca, Augustin M. Madalan, Rodolphe Cérac and Marius Andruh Contributions- 2 posters 2. First heterotrimetallic complexes using a 5d heteroleptic cyanido-metalloligand, autori: Maria-Gabriela Alexandru, Diana Visinescu, Augustin M. Madalan, Francisc Lloret, Miguel Julve and Marius Andruh 40 th International Conference on Coordination Chemistry, Valencia- 9-13 september, 2012 1. New families of heterotrimetallic nanomagnets, autori: Diana Visinescu, Maria-Gabriela Alexandru, Augustin M. Madalan, Marius Andruh, Jean-Pascal Sutter, Rodolphe Clérac and Ie-Rang Jeon Contributions- 4 posters 2. New 0-D heterotrimetallic Cu II -Mo(W) V -Ln III complexes. Structural and magnetic properties. Autori: Maria-Gabriela Alexandru, Diana Visinescu, Augustin M. Madalan, Rodolphe Clérac, Corine Mathonière, Marius Andruh 3. Heterodimetallic Zn II -Ln III complexes with tunable luminescent properties, Autori: Traian D. Pasatoiu, Augustin M. Madalan, Carmen Tiseanu and Marius Andruh. 4. Dodecanuclear [Cu 6 II Ln 6 III ] nanoclusters (Ln = Gd, Tb, Dy, Ho). A new magnetic refrigerant. Alina S. Dinca, Alberto Ghirri, Augustin M. Madalan, Marco Affronte, Francesc Lloret, Miguel Julve and Marius Andruh XXXII nd National Chemistry Conference, Caciulata, 3-5 october 2012 Contribution – one oral presentation Traian D. Pasatoiu, Augustin M. Madalan,Marius Andruh : Self-assembled octameric water clusters and infinite water tapes found in 3d-4f complexes with hexadentate Schiff-base ligands

17. RESULTS 2011-2012 2 Published articles [W(bipy)(CN) 6 ] − : A Suitable Metalloligand in the Design of Heterotrimetallic Complexes. The First Cu II Ln III W V Trinuclear Complexes, M.-G. Alexandru, D. Visinescu, A. M. Madalan, F. Lloret, M. Julve, M. Andruh, Inorg. Chem., 2012, 51, 4906 I.F. = 4.593 *, 15 citations ** 2. Self-assembly of [Cu II Tb III ] 3+ and [W(CN) 8 ] 3− tectons: a case study of a mixture containing two complexes showing slow-relaxation of the magnetization, D. Visinescu, I.-R. Jeon, A. M. Madalan, M.-G. Alexandru, B. Jurca, C. Mathonière, R. Clérac, M. Andruh, Dalton T., 2012, 41, 13578. I. F. = 3.806 *, 5 citations ** 1 submitted article Low-Dimensional 3d-4f Complexes Assembled from Low-Spin [Fe III (phen)(CN) 4 ] - Anions, D. Visinescu, L. M. Toma, O. Fabelo, C. Ruiz-Pérez, F. Lloret, M. Julve PUBLICATIONS * I. F. represents the impact factor of the scientific journal in 2012 according to ISI Thompson, Journal Citation Report **The number of citations up to date (excluding self-citations)

18. No. BUDGET CHAPTER (EXPENSES) TOTAL 2012 (lei) 1.SALARIES100000 2.OVERHEAD49996.47 3.MOBILITY51064 4. INVENTORY 98939.53 TOTAL300000 BUDGET 2011-2012 No. BUDGET CHAPTER (EXPENSES) TOTAL 2011 (lei) 1.SALARIES20000 2.OVERHEAD10003.53 3.MOBILITY0 4. INVENTORY 29996.47 TOTAL60000

19. 2013  Design of (photo)magnetic heterotrimetallic complexes Synthesis, crystallization and preliminary characterization of new precursors Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU Dr. Traian Dinu PASATOIU Dr. Gabriela MARINESCU Andrei Alunel Patrascu, M. Sc. Student Lewis Acids Lewis Basis {Co II -M V /Fe III } {Cu II /Mn II -M IV } Photomagnetic properties

20. [Mo IV (bipy)(CN) 3 O] - [W IV (bipy)(CN) 6 ] 2- 2013 Synthesis, cristallization and characterization of new 3(4,5)d metalloligands Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU [Fe III (phen)(CN) 4 ] -

21.  M T vs. T plot for structural type 1 (Ln = Gd). Inset: magnetization vs H plot for Gd derivative at 2.0 K. 2013 2,2’-bipyrimidine + Reactivity of [Fe(phen)(CN) 4 ] - toward Ln(III) ions Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU Prof. Miguel JULVE Prof. Francesc LLORET Type 1 Type 2 The reactivity of [Fe III (phen)(CN) 4 ] - anion against lanthanide(III) ions has been tested in order to use the tetracyano- heteroleptic unit to assemble 3d-4f-3d’ heterotrimetallic complexes (phen = 1,10-phenantroline). This work has been done in colaboration with the University of Valencia.

22. [Cu I (CN) 3/2 ] 1/2- [{Cu II (tren)} 2 (  -CN)] 3+  M T (o) and  M (∆) against T plots for the cyanide- based clathrate. The solid line is the best-fit curve. Reactivity of [W IV (CN) 4 O 2 ] - toward Cu(II) ions 2013 A new 5d cyano-based metalloligand, [W IV (CN) 4 O 2 ] 4- in order to design photomagnetic heterotrimetallic molecular materials. Prof. Miguel JULVE Prof. Francesc LLORET Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU A new 5d tetracyano-tungstate(IV) precursor, with the formula [W IV (CN) 4 O 2 ] 4-, has been synthesized and tested in reaction with copper(II) cationic complexes. The in situ hydrolisis of the tetracyanometallate complex led to unexpected results. The released cyanide groups has reacted with copper(II) ions and tren [tren = tris(2- aminoethyle)amine] ligand to finally afford a unique cyano- based clathrate, namely [Cu I 2 (CN) 3 ][{Cu II (tren)} 2 (  - CN)](CF 3 SO 3 ) 2. Perspective view of the ionic inclusion compound

23. Training school 9-22 june 2013 – participation to The Zürich Crystallography School (5 th edition), held in Institute of Organic Chemistry at the University of Zürich, Switzerland 22 june-4 august 2013 – research stage at ICMol, Universitat de Valencia-Prof. Miguel Julve The aim of the school was to provide the essential theory and practice of small-molecule single-crystal X-ray crystallography. The course was also a hands-on approach to crystallography, offering the opportunity to measure and solve the structure of single-crystals brought by each participant, after learning the basics in crystallography. The practical/theoretical knowledge offered by the intensive crystallography school is extremely important in order to perform X-ray diffraction measurements on single-crystals and to analyze the dataset for a complete structural characterization of complexes and also for a better understanding of their magnetic behaviour. Diana Visinescu and Maria-Gabriela Alexandru 2013 Synthesis of new heteroleptic 4(5)d cyano-based metalloligands. Testing the reactivity of the new obtained metallocyanates against cationic complexes. Structural and DC/AC magnetic measurements of the obtained precursors and compounds. Preparing of manuscripts. Research stage

24. Conferences 18 th Romanian International Conference on Chemistry and Chemical Engineering, RICCCE XVIII, 4-7 september 2013, Sinaia Towards heterotrimetallic nanomagnets, D. Visinescu, M.-G. Alexandru, A. Madalan and M. Andruh, oral communication International Conference of Physical Chemistry-ROMPHYSCHEM 15, 11-13 september 2013, Bucharest New polymetallic systems obtained using anions of organic acids as spacers, Traian D. Pasatoiu, Augustin M. Madalan, Marius Andruh, oral communication New molecular-based magnetic materials. D. Visinescu, M.-G. Alexandru, A. Madalan, B. Jurca, M. Andruh, J.P. Sutter and R. Clérac, oral communication RESULTS 2013 Contributions- 2 oral presentations Contribution - one oral presentation

25. RESULTS2013 Two published article 1.Low-Dimensional 3d–4f Complexes Assembled by Low-Spin [Fe III (phen)(CN) 4 ] − Anions, Diana Visinescu, Luminita Marilena Toma, Oscar Fabelo, Catalina Ruiz-Pérez, Francesc Lloret, and Miguel Julve, Inorg. Chem. 2013, 52, 1525-1537. I.F. = 4.794 *, 4 citations ** 2. Synthesis, crystal structure and magnetic properties of a new cyanide-bridged mixed- valence copper(I)/copper(II) clathrate, Diana Visinescu, Oscar Fabelo, Catalina Ruiz-Pérez, Francesc Lloret, and Miguel Julve, Inorg. Chem. Commun., 2013, 35, 252-254. I.F. = 2.062 * Publications * I. F. represents the impact factor of the scientific journal in 2013 according to ISI Thompson, Journal Citation Report **The number of citations up to date (excluding self-citations)

26. No. BUDGET CHAPTER (EXPENSES) TOTAL 2013 (lei) 1.SALARIES150.127,04 2.OVERHEAD50.000,00 3.MOBILITY35.125,38 4. INVENTORY 64.747,58 TOTAL300.000,00 BUDGET 2013 * * 5.34 % of the total sum in 2013 was redistributed

27. 2014  Design of 3d-3d’-5d heterotrimetallic complexes with photomagnetic properties Synthesis, crystallization and preliminary characterization of new precursors Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU Dr. Traian Dinu PASATOIU Dr. Gabriela MARINESCU Andrei Alunel Patrascu, M. Sc. Student Lewis Acids Lewis Basis

28. 2014 Synthesis, crystallization and characterization of new heterotrimetallic complexes with potential photomagnetic properties CuMnW Dr. Diana Beatrice VISINESCU Dr. Maria Gabriela ALEXANDRU

29. 2014Structural analysis of the compounds Zig-zag chain Hydrogen-bonds -CN  HO-CH 3 Supramolecular layers Magnetic properties in progress Dr. Rodolphe Clérac Dr. Corine Mathonière

30. Conferences The 14 th International Conference on Molecular-based Magnets ICMM, Saint Petersburg, Russia, 5-9 iulie 2014 Model compounds for the study of the exchange interaction in Cu II Ln III M V heterotrimetallics (Ln = La, Gd, Tb; M = Mo, W), D. Visinescu, M.-G. Alexandru, A. M. Madalan, C. Maxim, C. Matonière, R. Clérac and M. Andruh, oral presentation Two-dimensional {Ni(II)Ln(III)Fe(III)} heterotrimetallic coordination polymers, M.-G. Alexandru, D. Visinescu, N. Marino, G. DeMunno, J. Vallejo, F. Lloret, M. Julve and M. Andruh, poster presentation New heterotrimetallic nanomagnets, D. Visinescu, M.-G. Alexandru, A. M. Madalan, R. Clérac, J.-P. Sutter, Marius Andruh, poster presentation 8eme Colloque Franco-Roumaine de Chimie Apliqueé (CoFrRoCA), Montpellier, 15-18 september 2014 Results 2014

31. No. BUDGET CHAPTER (EXPENSES) TOTAL 2014 (lei) 1.SALARIES50.240,80 2.OVERHEAD15.000,00 3.MOBILITY13.079,94 4. INVENTORY 11.679,26 TOTAL90.000,00 * 3.69 % of the total sum in 2014 was redistributed 2014*