REASERCH PROJECTS for YOUNG RESEARCH TEAMS

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. Traian Dinu PASATOIU


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


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.


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. Traian Dinu PASATOIU


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*

REASERCH PROJECTS for YOUNG RESEARCH TEAMS

Documents

Transcript of REASERCH PROJECTS for YOUNG RESEARCH TEAMS