Multifunctional organic stable radicals in supramolecular high-spin architectures and materials

This work is supported by a Grant of the Romanian National Authority for Scientific Research, CNCS - UEFISCDI.

Project No. 87/5.10.2011 Code: PNII-ID-PCE-2011-3-0408
October 2011-September 2016

Project Summary

New multifunctional organic stable free (poly)radicals of different types will be obtained and used as building blocks for supramolecular architectures and materials with high-spin properties. The synthesis of such radicals (organic spins) will be conducted in a way to achieve in the same molecule tailored moieties that can be involved in supramolecular bonds (H-bonds, pi-stacking, donor-acceptor, charge-transfer, etc.). Thus, the new compounds may contain aromatic-, polynitro-, urea-, amino-, carboxyl-, or macrocyclic crown ether moieties, which are well known to form supramolecular architectures. These multifunctional (poly)radicals will be used to build supramolecular assemblies through non-covalent bonds, resulting supramolecular systems that can act as high-spin materials, due to co-operative spin-spin interactions. Cucurbiturils, a category of macrocyclic compounds containing urea moieties, will be used to control the size and stability of the supramolecular architectures, tuning the spin-spin interactions. Different types of nanoparticles labelled with organic spins will be also obtained and involved in supramolecular architectures. Classical organic chemistry and analytical measurements will be used for the design and full characterization of the new compounds, as well for their supramolecular assemblies; (para)magnetic measurements will provide information about spin distribution, inter-spin distance and exchange, and magnetic behaviour.

Team:

Ionita Petre
Caproiu Miron
Zalaru Christina
Zarafu Irina
Ionita Elena
Paraschivescu Codruta
Marinescu Maria
Nica Simona
Dumitru Ioana
Paun Anca
Remes Cristina

Project leader
Senior Researcher
Senior Researcher
Senior Researcher
Senior Researcher
Postdoc
Postdoc
Postdoc
Ph. D Student
Ph. D Student
Master Student

Scientific goals and objectives:

• Synthesis of stable free (poly)radicals containing groups that are known to induce the formation of supramolecular assemblies; full characterization of the new compounds (and their precursors) by appropriate techniques;

• Studies regarding the formation/stability of host-guest inclusion complexes using cucurbiturils and the new (poly)radicals;

• Supramolecular assemblies between different types of (poly)radicals;

• Evaluation of the physical and chemical properties (electronic, magnetic, etc.) of the molecules and their supramolecular architectures; possible applications as tunable organic magnetic materials, quantum electronic devices, markers and sensors.

Budget:

BUDGET (RON)	2011	2012	2013	2014	2015	2016	TOTAL
PERSONELL	45000	406778.9	134996.57	89964.52	100660.8	122560.3	899961.09
OVERHEADS	13261.42	139250	39494.03	30000	25165.2	52829.35	300000
MOBILITIES	0	15974.47	2951.01	1169.34	0	29025.53	49120.35
LOGISTICS	7988.58	134246.63	20085.64	28866.14	0	59731.57	250918.56
TOTAL	66250	696250	197527.25	150000	125826	264146.75	1500000

Results:

15. Covalently grafted TEMPO on graphene oxide: a composite material for selective oxidations of alcohols, A. J. Shakir, D. C. Culita, J. C. Moreno, A. Musuc, O. Carp, G. Ionita, P. Ionita, Carbon, 2016, 105, 607-614.

14. Synthesis of novel TEMPO stable free (poly)radicals derivatives and their host-guest interaction with cucurbit[6]uril, G. Ionita, A. M. Madalan, A. M. Ariciu, A. Medvedovici, P. Ionita, New J. Chem., 2016, 40, 503-511.

13. Exploring porous nanosilica-TEMPO as heterogeneous aerobic oxidation catalyst. The influence of supported gold clusters, A. Shakir, M. Florea, D. C. Culita, G. Ionita, C. Ghica, C. Stavarache, A. Hanganu, P. Ionita, J. Porous. Mat., 2016, 23, 247-254.

12. A convenient alternative for the oxidation of various alcohols by silica supported TEMPO free radical using nitrosonium tetrafluoroborate as cocatalyst, A. Shakir, C. Paraschivescu, M. Matache, M. Tudose, A. Mischie, F. Spafiu, P. Ionita, Tetrahedron Let., 2015, 56, 6878-6881.

11. Silver azide nanoparticles embedded into silica as energetic nano-materials, C. Ghica, R. Damian, D. Culita, I. Turcu, P. Ionita, Mat. Sci., 2015, 21, 329-332.

10. An EPR spin-trapping study of free radicals in cigarette smoke, A. M. Ariciu, P. Ionita, G. Ionita, Rev. Roum. Chim., 2014, 59, 781-789.

9. Thermal behavior of several stable hydrazyl free radicals and of their parent hydrazines, M. Marinescu, C. Zalaru, M. Florea, P. Ionita, J. Thermal Analysis Calorim., 2014, 116, 259-263.

8. A QSPR Study on Some Hydrazyl Radicals and Congeners, M. Marinescu, C. Zalaru, P. Ionita, Sci. Bull., 2014, 76, 175-184.

7. A mechanistic glimpse on the oxidation of alcohols using TEMPO/NOx catalytic systems: towards a greener bifunctional catalyst, P. Ionita, RSC Advances, 2013, 3, 21218-21221.

6. Synthesis and structural characterization of a stable betaine imino-nitroxide free diradical, A. Paun, I. Zarafu, M. T. Caproiu, P. Ionita, Arkivoc, 2013, iv, 144-151.

5. Synthesis and microbiological evaluation of several benzocaine derivatives, A. Paun, I. Zarafu, M. T. Caproiu, C. Draghici, M. Maganu, A. I. Cotar, M. C. Chifiriuc, P. Ionita, Comptes Rendu Chimie, 2013, 16, 665-671.

4. An enhanced colorimetric chemosensor for the detection of various nitro-explosives, P. Ionita, Tetrahedron Let., 2012, 53, 7143-7146.

3. Reversible aggregation between nanoparticles induced by acid-base interactions, G. Ionita, C. Ghica, I. Turcu, P. Ionita, Chem. Phys. Let., 2012, 546, 133-135.

2. EPR spectra of a mono- and a hetero di-radical in nematic and isotropic phases, G. Ionita, I. Zarafu, A. Paun, P. Ionita, Mol. Cryst. Liq. Cryst., 2012, 562, 141-146.

1. Chemical and biological evaluation of some new antipyrine derivatives with particular properties, C. Remes, A. Paun, I. Zarafu, M. Tudose, M. T. Caproiu, G. Ionita, C. Bleotu, L. Matei, P. Ionita, Bioorganic Chemistry, 2012, 41-42, 6-12.

Raport activitate 2011-2016
Scientific report 2011-2016 (english)