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
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.
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.
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 PASATOIU
2011-2012 – 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*
National and International Collaborations
Acad. Marius ANDRUHUniversity 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 SPANIAProf. 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
FTIR SPECTROMETERJASCO -4100400-4000 cm-1
Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy
UV-Vis SPECTROMETERPERKIN-ELMER LAMBDA
L35, 200-1100 nm
JASCO FP-8300 SPECTROFLUORIMETER
200-650 nm
INCUBATOR Memmert UNB500
MAIN RESEARCH FACILITIES
University of Bucharest, Faculty of Chemistry
MAIN RESEARCH FACILITIES
X-ray diffractometer on single-crystals
STOE IPDS II
Cryogenic SQUID magnetometer
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
Synthesis, cristallization and preliminary characterization of heterotrimetallic complexes
2011-2012
3d-4f-3(4,5)dHeterotrimetallic systems
Dr. Diana Beatrice
VISINESCU
Dr. Maria Gabriela
ALEXANDRU
Drd. Traian Dinu PASATOIU
2011-2012Structural characterization of the obtained compounds
Single-crystal X-ray diffraction
Dr. Augustin Madalin
MADALAN
University of Bucharest
O
OHN
N OH
O
H2valpn
1-D
0-D
[M’(CN)8]3- (M = Mo, W)
[W(bipy)(CN)6]-
MII = Cu; LnIII = La, Ce, Eu, Gd, Tb, Dy, HoMV = Mo, W
MII = Cu; LnIII = Gd, Tb, Ho
2011-2012
H2valdp
0-D
1-D
H2valen
1-D
MII = Cu; LnIII =La, Eu, Sm, Nd, Gd, Tb, Dy; MV = Mo, W
O
OHN
N OH
O
[M’(CN)8]3- (M = Mo, W)
{CuIITbIIIWV}
MII = Cu; LnIII = Gd, Tb, Dy; MV = Mo; LnIII = La, Gd, Tb, Dy; MV = W
MII = Cu; LnIII = La, Pr; MV = Mo
Structural characterization of the obtained compounds
2011-2012The analysis of the magnetic properties of the obtained compounds
Dr. Rodolphe CléracDr. Corine Mathonière
SCM
= 110-9 sUeff = 53.9K
{CuIITbIIIMoV}
SMM
Powder X-ray diffraction:
2011-2012 Structural characterization of the obtained compounds
Dr. Bogdan Ciprian
JURCA
University of
Bucharest
Chain:trinuclear 1:8
2011-2012 Magnetic properties
Dr. Jean-Pascal SUTTER
{CuIITbIIIMoV}{CuIITbIIIWV}
HDC = 3000 Oe
Prof. Miguel JULVEProf. Francesc LLORET
7
8
9
0 100 200 300
MT
/ cm
3 mol
-1 K
T / K
0
2
4
6
8
10
0 1 2 3 4 5 6 7
M /
H / T
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 SutterAC 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.
RESULTS 2011-2012
National and International Conferences
Vth 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 Andruh40th 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 CuII-Mo(W)V-LnIII complexes. Structural and magnetic properties. Autori: Maria-Gabriela Alexandru, Diana Visinescu, Augustin M. Madalan, Rodolphe Clérac, Corine Mathonière, Marius Andruh3. Heterodimetallic ZnII-LnIII complexes with tunable luminescent properties, Autori: Traian D. Pasatoiu, Augustin M. Madalan, Carmen Tiseanu and Marius Andruh.
4. Dodecanuclear [Cu6IILn6
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 AndruhXXXIInd National Chemistry Conference, Caciulata, 3-5 october 2012
Contribution – one oral presentationTraian 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
RESULTS 2011-2012
2 Published articles
[W(bipy)(CN)6]−: A Suitable Metalloligand in the Design of Heterotrimetallic Complexes. The
First CuIILnIIIWV 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 [CuIITbIII]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 [FeIII(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)
No. BUDGET CHAPTER (EXPENSES)TOTAL2012(lei)
1. SALARIES 100000
2. OVERHEAD 49996.47
3. MOBILITY 51064
4.INVENTORY
98939.53
TOTAL 300000
BUDGET 2011-2012
No. BUDGET CHAPTER (EXPENSES)TOTAL2011(lei)
1. SALARIES 20000
2. OVERHEAD 10003.53
3. MOBILITY 0
4.INVENTORY
29996.47
TOTAL 60000
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
{CoII-MV/FeIII}
{CuII/MnII-MIV}
Photomagnetic properties
[MoIV(bipy)(CN)3O]- [WIV(bipy)(CN)6]2-
2013
Synthesis, cristallization and characterization of new 3(4,5)d metalloligands
Dr. Diana Beatrice
VISINESCU
Dr. Maria Gabriela
ALEXANDRU
[FeIII(phen)(CN)4]-
MT 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 JULVEProf. Francesc LLORET
Type 1Type 2
The reactivity of [FeIII(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.
[CuI(CN)3/2]1/2-
[{CuII(tren)}2(-CN)]3+
MT (o) and M (∆) against T plots for the cyanide-based clathrate. The solid line is the best-fit curve.
Reactivity of [WIV(CN)4O2]- toward Cu(II) ions2013
A new 5d cyano-based metalloligand, [WIV(CN)4O2]4- in order to design photomagnetic heterotrimetallic molecular materials.
Prof. Miguel JULVEProf. Francesc LLORET
Dr. Diana Beatrice
VISINESCU
Dr. Maria Gabriela
ALEXANDRU
A new 5d tetracyano-tungstate(IV) precursor, with the formula [WIV(CN)4O2]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 [CuI
2(CN)3][{CuII(tren)}2(-CN)](CF3SO3)2.
Perspective view of the ionic inclusion compound
Training school
9-22 june 2013 – participation to The Zürich Crystallography School (5th 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
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
Conferences
18th 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
RESULTS 2013
Two published article
1. Low-Dimensional 3d–4f Complexes Assembled by Low-Spin [FeIII(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)
No.BUDGET CHAPTER (EXPENSES)
TOTAL2013(lei)
1. SALARIES 150.127,04
2. OVERHEAD 50.000,00
3. MOBILITY 35.125,38
4.INVENTORY
64.747,58
TOTAL 300.000,00
BUDGET 2013*
* 5.34 % of the total sum in 2013 was redistributed
20142014 Design of 3d-3d’-5d heterotrimetallic complexes with photomagnetic
propertiesSynthesis, 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
2014
Synthesis, crystallization and characterization of new heterotrimetallic complexes with potential photomagnetic properties
CuMnW
2180 2160 2140 2120 2100 20800.00
0.05
0.10
0.15
0.20
a.u.
cm-1
(A) W(V) W(IV)
Dr. Diana Beatrice
VISINESCU
Dr. Maria Gabriela
ALEXANDRU
2014 Structural analysis of the compounds
Zig-zag chain
Hydrogen-bonds
-CNHO-CH3
Supramolecular layers
Magnetic properties in progress
Dr. Rodolphe CléracDr. Corine Mathonière
Conferences
The 14th International Conference on Molecular-based Magnets ICMM, Saint Petersburg, Russia, 5-9 iulie 2014
Model compounds for the study of the exchange interaction in CuIILnIIIMV
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
No.BUDGET CHAPTER (EXPENSES)
TOTAL2014(lei)
1. SALARIES 50.240,80
2. OVERHEAD 15.000,00
3. MOBILITY 13.079,94
4.INVENTORY
11.679,26
TOTAL 90.000,00
* 3.69 % of the total sum in 2014 was redistributed
2014*