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PROCESE DE AUTOASAMBLARE A
MATERIALELOR MOLECULARE LUMINESCENTE
Rezumat
Prezentul proiect isi propune sa dezvolte un studiu sistematic al sintezei si proprietatilor
fotofizice ale sistemelor metal-supramoleculare obtinute prin utilizarea urmatoarelor tipuri de
luminofori sau a combinarii lor in cadrul aceleasi entitati moleculare/supramoleculare:
a) sisteme complexe construite cu ioni de Zn(II), Cd(II) (configuratie electronica d 10) si liganzi
compartimentali de tip baza Schiff, in care luminescenta provine preponderent de la scheletul
organic; b) complecsi continand ioni trivalenti de lantanide Ln(III) (ioni 4f luminescenti in
domeniul vizibil Tb(III), Eu(III), sau in domeniul infrarosu apropiat (NIR) Pr(III), Nd(III), Er(III),
Yb(III)); c) sintoni supramoleculari formati prin interactiuni metalofile (d 8 - d8, d10 - d10).
Obiectivele majore ale proiectului sunt: construirea de retele cristaline luminescente
continand trei grupari luminofore (cromofori d10, 4f si, respectiv, interactiuni metal-metal d 10d10) si obtinerea de sisteme homo- si heterometalice chiral-luminescente prin auto-asamblare
de unitati metalice luminescente cu diversi conectori organici chirali. Exista posibilitatea
cooperarii intre aceste proprietati (fluorescente si optice) in sensul crearii unor sisteme
supramoleculare multifunctionale. Sistemele supramoleculare obtinute vor fi caracterizate prin
difractie de raze X pe monocristal, prin diferite metode fizico chimice (spectroscopie IR,
UV-VIS, NIR) si speciale, in functie de proprietatile manifestate (fluorescenta, magnetism).
Imbinarea judicioasa a diferitelor proprietati si caracteristici deschide calea unor aplicatii de
interes ale acestor sisteme multimetalice.
Obiective majore
Sinteza rationala de sisteme supramoleculare luminescente construite pe
baza
de
tectoni
homosi
heterometalici
d10-d10,
d10-4f,
4f-4f si 4f-4f.
Obtinerea de sisteme homo- si heterometalice chiral-luminescente prin autoasamblare de unitati metalice si conectori organici chirali.
Design de arhitecturi supramoleculare heterometalice utilizand doua surse
de luminescenta (luminofori d10 sau 4f si, respectiv, interactiuni metalofile d8d8, d10-d10).
Construirea de retele cristaline luminescente continind trei grupari
luminofore (cromofori d10, 4f si, respectiv, interactiuni metal-metal d10-d10);
compusii rezultanti ar reprezenta o premiera in domeniul combinatiilor
complexe luminescente .
Investigarea proprietatilor luminescente ale noilor sisteme moleculare
obtinute; Corelatii magneto-structurale in cazul sistemelor care contin ioni
metalici paramagnetici (in special, ionii Ln(III)).
Echipa de cercetare
Titlul
didactic
stiintific
Anul
nasterii
Doctorat
Marinescu Gabriela
1972
Cercetator
Stiintific III
Da
Gheorghe Ruxandra
Florina
1976
Lector
Da
1974
Cercetator
Stiintific III
Da
1973
Lector
Da
1979
Cercetator
Da
1981
Doctorand
Structura buget
NR.
CRT
TOTAL
VALOARE 2009
(lei)
TOTAL
VALOARE 2010
(lei)
TOTAL
VALOARE 2011
(lei)
TOTAL
VALOARE
(lei)
58675
105000
140000
303675
16006,2
27500
46600
90106,2
2100
15000
17100
proiectului
(infrastructura de cercetare, cheltuieli materiale, diseminare etc.)
30361
40400
78400
149161
TOTAL
105042,2
175000
280000
560042,2
1.
2.
total a contractului
MOBILITI
3
4.
5.
Lucrari reprezentative:
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, L. Diamandescu, Rev. Roum. Chim. 2010, 55(2), 131-135.
10. D.C. Culita G. Marinescu, L Patron, F. Tuna, N. Stanica, Ma Yun, Rev. Roum. Chim. 2010, 55(1),63-67.
11. G. Marinescu, G. Marin, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, Cryst. Growth & Design 2010, 10, 2096-2103.
12. G. Marinescu, M. Andruh, F. Lloret, M. Julve, Coord. Chem. Rev. 2010, accepted.
Publicatii semnificative:
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 (NMP3CT-2005-515767) FP6, MAGMANet NoE, 2006, 106-107.
3. R Gheorghe, M. Andruh, J.-P. Costes, B. Donnadieu, M. Schmidtmann, A. Mller, 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. WileyVCH).
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. Brnzea, R. Gheorghe, A.M. Mdlan, Cryst. Eng. Comm. 2009, 11, 2571-2584(Ed. Royal Society of Chemistry).
9. R. Gheorghe, A.M. Madalan, J.P. Costes, W. Wernsdorfer, M. Andruh, Dalton Trans., 2010, 39, 4734-4736
Domenii de competenta:
Chimia coordinativ, Chimia metalelor, Stereochimia compuilor coordinativi, Chimia supramolecular, Biomolecule
anorganice, Compui anorganici cu aciune terapeutic.
LUCRARI RECENTE:
1.
7.
8.
G. Marin, M. Andruh, A. M. Madalan, A. J. Blake, C. Wilson, N. R. Champness, M.Schrder, Cryst. Growth & Design, 2008, 8, 964975.
A. M. Madalan, N. Avarvari, M. Fourmigu, R. Clrac, L. F. Chibotaru, S. Clima, M. Andruh, Inorg. Chem., 2008, 47, 940-950.
C. Ene, A. M. Madalan, C. Maxim, B. Jurca, N. Avarvari, M. Andruh, J.A.C.S., 2009, 131, 4586-4587.
D. G. Branzea, R. Gheorghe, A. M. Madalan, M. Andruh, Cryst. Eng. Comm., 2009, 11, 2571-2584.
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, 15, 11808- 11814.
A. M. Madalan, C. Rthor, M. Fourmigu, E. Canadell, E. B. Lopes, M. Almeida, P. Auban-Senzier, N. Avarvari, Chem. Eur. J., 2010,
16, 528-537.
V. Tudor, A. Madalan, V. Lupu, F. Lloret,M. Julve, M. Andruh, Inorg. Chim. Acta, 2010, n curs de publicare.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, Inorg. Chem. 2010, 49, 2310-2315.
9.
10.
11.
R. Gheorghe, A.M. Madalan, J.P. Costes, W. Wernsdorfer, M. Andruh, Dalton Trans., 2010, 39, 4734-4736
T.D. Pasatoiu, M. Etienne, A.M. Madalan, M. Andruh, R. Sessoli, Dalton Trans., 2010, 39, 4802-4808.
G. Marinescu, G. Marin, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, Cryst. Growth & Design 2010, 10, 2096-2103.
2.
3.
4.
5.
6.
Domenii de competenta:
-strategii de sinteza (node and spacer, building block) ale combinatiilor complexe homo- si heteropolinucleare de dimensionalitate
controlata (chimia combinatiilor complexe polinucleare); -sinteza de liganzi polidentati si utilizarea lor in design-ul de sisteme
polimetalice (chimie organica); -arhitecturi supramoleculare polimetalice realizate pe baza diverselor interactii supramoleculare
legaturi de hidrogen, interactii - stacking, interactii metalofile - (chimia supramoleculara); -tehnici experimentale de investigare
structurala (difractie de raze X, spectroscopie IR, UV-Vis, NIR) si a proprietatilor combinatiilor complexe (masuratori criomagnetice);
-prelucrarea datelor experimentale cu ajutorul diverselor programe - Kaleidagraph, Origin, Diamond, XP si interpretarea datelor
obtinute.
LUCRARI:
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, 333339.
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.
4. M. Andruh, D.G. Brnzea, R. Gheorghe, A.M. Mdlan, Cryst. Eng. Comm. 2009, 11, 2571-2584.
Studii: Iunie 2000 Colegiul National Al. D. Ghica, Alexandria; 2004 Licenta, Facultatea de Chimie, Universitatea din Bucuresti,
specializarea Chimie in limba engleza; 2006 Master in Chimie Coordinativa, Universitatea din Bucuresti; Oct. 2006 a.c.
Facultatea de Chimie, Universitatea din Bucuresti, doctorand cu frecventa, conducator stiintific Prof. Marius Andruh; In octombrie
2006, in baza colocviului de admitere la doctorat in cadrul Scolii Doctorale in Chimie, din cadrul Univerisitatii din Bucuresti,
Facultatea de Chimie, a fost admis ca doctorand cu frecventa, cu tema tezei: Combinatii complexe heteropolinucleare ce contin 3
purtatori de spin diferiti: 3d-4f-4d sau 3d-4f-5d, conducator stiintific Profesor Marius Andruh.
Competente:
Chimia si proprietatile magnetice ale complecsilor polinucleari, Chimie supramoleculara, Metode fizico-chimice de
investigare a structurii compusilor chimici; Cunostinte hardware, Microsoft Office, software pentru prelucrarea rezultatelor
experimentale (Chemoffice, Kaleidagraph, Diamond, BIORAD Merlin).
LUCRARI:
1.
2.
3.
4.
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.
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.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, Inorg. Chem. 2010, 49, 2310-2315.
T.D. Pasatoiu, M. Etienne, A.M. Madalan, M. Andruh, R. Sessoli, Dalton Trans., 2010, 39, 4802-4808.
Rezultate
G. Marinescu, G. Marin, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, New molecular rectangles
and coordination polymers constructed from binuclear phenoxo-bridged [Cu2] and [Zn2] tectons, Crystal
Growth & Design. 2010, 10, 2096-2103.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, Temperature switching of LMCT role:
From quenching to sensitivation of europium emission in a Zn II-EuIII Binuclear Complex, Inorg. Chem.
2010, 49, 2310-2315.
G. Marinescu, A.M. Madalan, A. Vezeanu, M. Andruh, C. Tiseanu, New coordination polymers constructed
from binuclear phenoxo-bridged [Zn2] tectons, The 14th International Conference of Physical
Chemistry, ROMPHYSCHEM 14, June 2-4 2010, Bucharest, Romania.
T.D. Pasatoiu, A.M. Madalan, C. Tiseanub, M. Andruh, First SmIII Complex Exhibiting Two-Photon Induced
Fluorescent Emission, 7th International Conference of the Chemical Societies of the South-Eastern
European Countries on Chemistry Beauty and Application, September 15-17 2010, Bucharest,
Romania.
G. Marinescu, A.M. Madalan, M. Andruh, C. Tiseanu, Structures and photophysical properties of d10-metal
coordination polymers based on the Schiff base ligands, 7th International Conference of the Chemical
Societies of the South-Eastern European Countries on Chemistry Beauty and Application,
September 15-17 2010, Bucharest, Romania.
G. Marinescu, A.M. Madalan, M. Andruh, C. Tiseanu, New d10 heterometallic coordination polymers
based on compartmental Schiff-base ligands. Synthesis, structure and luminescence, submited to
Polyhedron, 2010.
T.D. Pasatoiu, A.M. Madalan, M. Andruh, C. Tiseanu, Heterodinuclear Complexes withy NLO Properties,
A XXXI-a Conferinta Nationala de Chimie 6-8 octombrie 2010, Ramnicu Valcea, Romania.
T.D. Pasatoiu, A.M. Madalan, M.U. Kumke, C. Tiseanu, M. Andruh, Fluorescent Emission of Europium in
Heterodinuclear ZnII-EuIII Complex, through Direct Excitation in the Visible Range, A XXXI-a Conferinta
Nationala de Chimie 6-8 octombrie 2010, Ramnicu Valcea, Romania.
R. Gheorghe, C. Tiseanu, M. Andruh, Study of the Luminiscent Properties of Homobinuclear 4f-4f
Complexes, submited to Journal of Luminescence, 2010.