Transcript towards a new generation of molecular magnetic materials

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, highstorage 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.
Objectives
The main objective is the obtaining of polynuclear structures incorporating three
different metal ions with enhanced magneto-optical properties (Scheme 1).
Specific objectives:
•
Design
and
synthesis
of
heterotrimetallic
nanomagnets
•
Scheme 1
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 magnetoluminiscent or magneto-chiral systems.
RESEARCH TEAM
Project leader:
Dr. Diana-Beatrice VISINESCU, Senior Researcher III
Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy
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
4. Dr. Augustin Madalin MADALAN Senior Researcher (lecturer), University of Bucharest
5. Dr. Bogdan Ciprian JURCA
Senior Researcher (lecturer), University of Bucharest
6. Alina Simona DINCA – Ph. D. student, University of Bucharest*
New research team members (from 1.06.2013):
Andrei Alunel PATRASCU – M. Sci. student, University of Bucharest*
Maria COCIS - technician, Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy
*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.
National and International Collaborations
University of Bucharest, Faculty of Chemistry
Acad. Marius ANDRUH
Institute of Macromolecular Chemistry “Petru
Poni”, Iasi Academia Romana
Dr. Sergiu SHOVA
Instituto de Ciencia Molecular (ICMol)
Universitat de València SPANIA
Prof. Miguel JULVE
Laboratoire de Chimie de Coordination, CNRS,
Université de Toulouse, FRANTA
Dr. Jean-Pascal SUTTER
Institut de Chimie de la Matiere Condensee
(ICMCB)/Centre de Recherche Paul Pascal CNRS, Université de Bordeaux, FRANTA
Dr. Rodolphe Clérac
Dr. Corinne Mathonière
MAIN RESEARCH FACILITIES
Institute of Physical Chemistry “Ilie Murgulescu”, Romanian Academy
FTIR SPECTROMETER
JASCO -4100
400-4000 cm-1
UV-Vis SPECTROMETER
PERKIN-ELMER LAMBDA
L35, 200-1100 nm
INCUBATOR Memmert UNB500
JASCO FP-8300
SPECTROFLUORIMETER
200-650 nm
MAIN RESEARCH FACILITIES
University of Bucharest, Faculty of Chemistry
X-ray diffractometer on single-crystals
STOE IPDS II
Cryogenic SQUID magnetometer
2011-2012
Design of heterometallic complexes exhbiting SMM or SCM properties
Synthesis, crystallization and characterization of precursors
3d-3d’ or 3d-4f heterometallic
complexes
LEWIS ACIDS
Polycyanometallates
Dr. Diana Beatrice VISINESCU
Oxalatometallates
Dr. Maria Gabriela ALEXANDRU
Dr. Gabriela MARINESCU
LEWIS BASIS
Drd. Traian Dinu PASATOIU
Drd. Alina Simona DINCA
2011-2012
Synthesis,
complexes
cristallization
and
preliminary
characterization
of
heterotrimetallic
3d-4f-3(4,5)d
Heterotrimetallic systems
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
Drd. Traian Dinu PASATOIU
2011-2012
Structural characterization of the obtained compounds
Single-crystal X-ray diffraction
[M’(CN)8]3- (M = Mo, W)
1-D
O
N
N
OH
MII = Cu; LnIII = La, Ce, Eu, Gd, Tb, Dy, Ho
MV = Mo, W
OH
O
[W(bipy)(CN)6]H2valpn
0-D
Dr. Augustin Madalin MADALAN
University of Bucharest
MII = Cu; LnIII = Gd, Tb, Ho
2011-2012
Structural characterization of the obtained compounds
[M’(CN)8]3- (M = Mo, W)
1-D
O
N
OH
N
OH
O
H2valen
0-D
{CuIITbIIIWV}
MII = Cu; LnIII =La, Eu, Sm, Nd, Gd, Tb, Dy; MV = Mo, W
1-D
MII = Cu; LnIII = Gd, Tb, Dy; MV = Mo;
LnIII = La, Gd, Tb, Dy; MV = W
H2valdp
MII = Cu; LnIII = La, Pr; MV = Mo
2011-2012 The analysis of the magnetic properties of the obtained compounds
{CuIITbIIIMoV}
SMM
SCM
 = 110-9 s
Ueff = 53.9K
Dr. Rodolphe Clérac
Dr. Corine Mathonière
2011-2012
Structural characterization of the obtained compounds
_
(211)
_
(141)
_
(121)
(012)
_
(101)
(111)
250
(120)
(011)
Powder X-ray diffraction:
200
150
experimental powder XRD pattern
100 Rietveld fit
50
20
simulated pattern for CuTbW-chain monoclinic ( P 21 ) phase
15
10
5
0
50
40
(040)
_
(111)
(Intensity)
1/2
(a.u.)
0
simulated pattern for CuTbW-trinuclear monoclinic ( P 21/n ) phase
30
20
10
Chain:trinuclear 1:8
0
5
6
7
8
9
10
11
13
12
2q (deg.)
14
15
16
17
18
19
20
Dr. Bogdan Ciprian JURCA
University of Bucharest
2011-2012
Magnetic properties
HDC = 3000 Oe
{CuIITbIIIMoV}
{CuIITbIIIWV}
Dr. Jean-Pascal SUTTER
M/
10

8
8
6
M
3
-1
 T / cm mol K
9
4
2
7
Prof. Miguel JULVE
Prof. Francesc LLORET
0
0
0
1
2
100
3
4
H/T
200
T/K
5
6
7
300
Internal and abroad short research stages
Diana Visinescu
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, 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
Contributions- 2 posters
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
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
40th International Conference on Coordination Chemistry, Valencia- 9-13 september, 2012
Contributions- 4 posters
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
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
Andruh
3. Heterodimetallic ZnII-LnIII complexes with tunable luminescent properties, Autori: Traian D. Pasatoiu,
Augustin M. Madalan, Carmen Tiseanu and Marius Andruh.
4. Dodecanuclear [Cu6IILn6III] 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
XXXIInd 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
RESULTS
2011-2012
PUBLICATIONS
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
* 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)
BUDGET 2011-2012
TOTAL
2011
(lei)
No.
BUDGET CHAPTER
(EXPENSES)
1.
SALARIES
20000
2.
OVERHEAD
10003.53
3.
MOBILITY
0
4.
INVENTORY
29996.47
TOTAL
60000
TOTAL
2012
(lei)
No.
BUDGET CHAPTER
(EXPENSES)
1.
SALARIES
100000
2.
OVERHEAD
49996.47
3.
MOBILITY
51064
4.
INVENTORY
TOTAL
98939.53
300000
2013
 Design of (photo)magnetic heterotrimetallic complexes
Synthesis, crystallization and preliminary characterization of new precursors
Lewis Acids
{CoII-MV/FeIII}
{CuII/MnII-MIV}
Photomagnetic
properties
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
Dr. Traian Dinu PASATOIU
Dr. Gabriela MARINESCU
Andrei Alunel Patrascu, M. Sc. Student
Lewis Basis
2013
Synthesis, cristallization and characterization of new 3(4,5)d metalloligands
[FeIII(phen)(CN)4]-
[MoIV(bipy)(CN)3O]-
[WIV(bipy)(CN)6]2-
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
2013
Reactivity of [Fe(phen)(CN)4]- toward Ln(III) ions
Type 1
Type 2
+
2,2’-bipyrimidine
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
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.
MT vs. T plot for structural type 1 (Ln = Gd).
Inset: magnetization vs H plot for Gd derivative
at 2.0 K.
Prof. Miguel JULVE
Prof. Francesc LLORET
2013
Reactivity of [WIV(CN)4O2]- toward Cu(II) ions
A new 5d cyano-based metalloligand,
heterotrimetallic molecular materials.
[WIV(CN)4O2]4-
in
order
to
design
photomagnetic
[CuI(CN)3/2]1/2-
[{CuII(tren)}2(-CN)]3+
0.003
Prof. Miguel JULVE
Prof. Francesc LLORET
0.4
M
M
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(2aminoethyle)amine] ligand to finally afford a unique cyanobased
clathrate,
namely
[CuI2(CN)3][{CuII(tren)}2(CN)](CF3SO3)2.
-1
3
0.002
3
c / cm mol
-1
0.6
Perspective view of the ionic inclusion compound
c T / cm mol K
0.8
0.001
0.2
0.000
0
100
T/K
200
0
300
MT (o) and M (∆) against T plots for the cyanidebased clathrate. The solid line is the best-fit curve.
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
Training school
2013
Diana Visinescu and Maria-Gabriela Alexandru
9-22 june 2013 – participation to The Zürich Crystallography School (5th edition), held in Institute of Organic
Chemistry at the University of Zürich, Switzerland
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.
Research stage
Diana Visinescu and Maria-Gabriela Alexandru
22 june-4 august 2013 – research stage at ICMol, Universitat de Valencia-Prof. Miguel Julve
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.
RESULTS 2013
Conferences
18th Romanian International Conference on Chemistry and Chemical Engineering, RICCCE XVIII, 4-7
september 2013, Sinaia
Contributions- 2 oral presentations
Towards heterotrimetallic nanomagnets, D. Visinescu, M.-G. Alexandru, A. Madalan and M. Andruh,
oral communication
New polymetallic systems obtained using anions of organic acids as spacers, Traian D. Pasatoiu,
Augustin M. Madalan, Marius Andruh, oral communication
International Conference of Physical Chemistry-ROMPHYSCHEM 15, 11-13 september 2013,
Bucharest
Contribution - one oral presentation
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
Publications
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 mixedvalence 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*
* 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)
BUDGET 2013*
TOTAL
2013
(lei)
No.
BUDGET CHAPTER
(EXPENSES)
1.
SALARIES
150.127,04
2.
OVERHEAD
50.000,00
3.
MOBILITY
35.125,38
4.
INVENTORY
TOTAL
64.747,58
300.000,00
* 5.34 % of the total sum in 2013 was redistributed
2014
 Design of 3d-3d’-5d heterotrimetallic complexes with photomagnetic properties
Synthesis, crystallization and preliminary characterization of new precursors
Lewis Acids
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
Dr. Traian Dinu PASATOIU
Dr. Gabriela MARINESCU
Andrei Alunel Patrascu, M. Sc. Student
Lewis Basis
2014
Synthesis, crystallization and characterization of new heterotrimetallic complexes with
potential photomagnetic properties
(A)
W(V)
W(IV)
0.20
a.u.
0.15
0.10
0.05
0.00
2180
2160
2140
2120
2100
2080
cm-1
CuMnW
Dr. Diana Beatrice VISINESCU
Dr. Maria Gabriela ALEXANDRU
2014
Structural analysis of the compounds
Zig-zag chain
Hydrogen-bonds
-CNHO-CH3
Magnetic properties in progress
Dr. Rodolphe Clérac
Dr. Corine Mathonière
Supramolecular layers
Results 2014
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
8eme Colloque Franco-Roumaine de Chimie Apliqueé (CoFrRoCA), Montpellier, 15-18 september 2014
New heterotrimetallic nanomagnets, D. Visinescu, M.-G. Alexandru, A. M. Madalan, R. Clérac, J.-P.
Sutter, Marius Andruh, poster presentation
2014*
TOTAL
2014
(lei)
No.
BUDGET CHAPTER
(EXPENSES)
1.
SALARIES
50.240,80
2.
OVERHEAD
15.000,00
3.
MOBILITY
13.079,94
4.
INVENTORY
TOTAL
11.679,26
90.000,00
* 3.69 % of the total sum in 2014 was redistributed