Research in our laboratory combines classical organic chemistry, supramolecular organic synthesis, coordination chemistry and crystal engineering at interface of fundamental research and material science.
Research topics:
Supramolecular assemblies developed through covalent and non-covalent interactions; design and synthesis of angular tectons employed in construction of 1-D, 2-D, and 3-D architectures.
Molecular magnetic materials designed using organic ligands selected rationally in order to favor magnetic interactions between metallic and/or organic spin carriers.
Molecular photoswitchers – design and synthesis of stimuli-responsive molecular materials by combining the photochromic units with azulene derivatives for development of smart switches.
Multifunctional materials – crystal engineering of electroactive organic and metal-organic cages; rational design of metal-organic frameworks for hydrogen isotope separation; design of extended π-conjugated systems for recognition of cationic and/or anionic species.
Covalent functionalization of graphenes for development of innovative electrodes within proton-exchange membrane fuel cell, by employing electrochemically active azulene moieties.
Heterospin molecular complexes - containing nitronyl nitroxide stable and persistent organic radicals and paramagnetic metal ions.
Fine organic synthesis and physico-chemical characterization of π-conjugated azulene-systems with non-linear optical properties or photoswitching ability; crystal engineering of supramolecular organic systems and metal-organic porous materials, self-assembling of electroactive organic building blocks; synthesis of organic cages and covalent organic frameworks; synthesis of fluorescent organic sensors able to recognize anionic/cationic species; design and synthesis of biologically active compounds.
Structural analysis of hydrazones comprising of azulene moieties, suitable for recognition of toxic cations (Hg, Cd, Pb), as well as of hydrazides obtained through association of azulene moieties with thioureido/ureido fragments, for the development of biological sensors using NMR spectroscopy; NMR spectroscopy studies for structural determination and interaction studies between chemical and biochemical compounds.
Synthesis and physico-chemical characterization of coordination compounds, ligand synthesis and coordination chemistry; development of novel supramolecular metal-containing assemblies; electrochemical investigations of multifunctional materials; host-guest investigations.
Organic synthesis of ligands and of coordination compounds; crystal engineering of covalent and non-covalent supramolecular assemblies, advanced physico-chemical characterization and spectroscopic investigations of multifunctional materials.
Research activities involving the synthesis and characterisation of mono- and polynuclear coordination compounds of d/f metals with Schiff base ligands.
Synthesis of organic compounds, stable organic nitronyl nitroxide radicals, polynuclear and heterospin coordination complexes (2p-3d, 2p-4f, 3d-4f, 2p-3d-4f, and 3d-4f-5d). Physico-chemical characterization of organic ligands and their coordination compounds. Crystal engineering. Single crystal and powder X-ray diffraction.
Design and synthesis of ligands and coordination compounds; physico-chemical characterization of molecules using standard techniques; beginner in the art of crystallization.
Synthesis of organic ligands and coordination compounds. Physico-chemical and spectroscopic characterization of ligands and their coordination products. Characterization of coordination compounds using single crystal and powder X-ray Diffraction.
Design and synthesis of coordination compounds with Schiff-base ligands: physico-chemical characterization of the obtained systems.
| Photo credit for all: Traian Pasatoiu |
Synthesis and characterization of ligands and coordination compounds based on Mannich and Schiff reactions and nitronyl nitroxide radicals.
His research is grounded in fine organic synthesis of optically active materials, targeting multiple forms of chirality: central, axial, and helical. A primary research direction focuses on the development of compartmental Schiff base–type ligands, designed to facilitate the transfer of chiral information to lanthanide ions. The ultimate objective is the induction of optical activity at the metal centers, enabling the generation of systems exhibiting circular dichroism (CD) and circularly polarized luminescence (CPL) properties. The activity further encompasses the synthesis of ligands displaying axial chirality and functionalized helicenes. Another research direction addresses the molecular engineering of organic materials functionalized with azulene units. The evaluation of photophysical properties is conducted using spectroscopic techniques (FT-IR, UV–Vis absorption and emission spectroscopy, CPL), investigated both in solution and in the solid state. Determination of emission quantum yields is performed, alongside structural elucidation through crystallographic data processing and NMR spectral interpretation. Expertise includes enantiomeric separation by HPLC and analytical determinations using HPLC/UHPLC-MS/MS techniques (Triple and Triple Quadrupole MS systems, Chromeleon software).
Her research activity focuses on the rational design and directed synthesis of complex molecular architectures, with particular emphasis on the use of Robson-type bicompartmental ligands for the preparation of functionalized homometallic binuclear precursors, aimed at the self-assembly of metal–organic cages exhibiting a [2+3] structural topology. In parallel, the field of interest includes the development of optically active coordination compounds based on Schiff base–type ligands and lanthanide ions derivatized with enantiopure amino acids, as well as the engineering of hydrogen-bonded organic frameworks (HOFs) employing azulene-based precursors for the generation of multifunctional materials. Spectroscopic characterization of the obtained systems, including FT-IR and UV–Vis spectroscopy, together with emission studies, is carried out to validate their photophysical properties, both in the solid state and in solution.
Her research addresses the design and organic synthesis of functionalized azulene precursors employed as building units in the self-assembly of palladiumbased metal–organic cages. The central objective is the development of multifunctional materials capable of exhibiting synergistic behavior between the intrinsic catalytic properties of the Pd centers and the electrochemically active and luminescent character of the azulene core. Physicochemical characterization of the obtained systems is performed, alongside expertise in thermogravimetric analysis.
The synthesis of nitronyl nitroxide radical–type ligands for the controlled elaboration of heterospin coordination compounds with defined magnetic properties.
The design and synthesis of optically active lanthanide coordination compounds employing Schiff base–type ligands derived from diketone precursors and enantiopure diamines. The primary objective is the transfer of chiral information to the metal ions. A second strategic direction focuses on the organic synthesis of multidentate ligands incorporating azulene units and tridentate coordination sites, designed for the assembly of molecular semiconductors. These systems are configured to modulate the spin-crossover (SCO) properties of the metal ions under the influence of external stimuli. Spectroscopic analysis (IR, UV–Vis absorption, and emission spectroscopy) of the obtained systems is performed.
The synthesis of luminescent organic cages employing self-assembly strategies based on dialdehydes incorporating structural motifs that promote emissive properties, together with dialdehyde precursors functionalized with carboxyl groups. The project aims to exploit the charge-transfer properties and emission efficiency of the corresponding structural fragments for the development of cavity-type supramolecular architectures. Characterization of the obtained systems is carried out through spectroscopic investigations.
Simona Nica - Guest editor for Frontiers in Chemistry, theme collection “Advances in the field of smart photochromic materials containing versatile molecular photoswitches” - https://www.frontiersin.org/research-topics/39791/advances-in-the-field-of-smart-photochromic-materials-containing-versatile-molecular-photoswitches
Covers:
“One-dimensional coordination polymers constructed from di- and tri-nuclear {3d–4f} tectons.A new useful spacer in crystal engineering: 1,3-bis(4-pyridyl)azulene”, A. E. Ion, S. Nica, A.M. Madalan, C. Maxim, M. Julve, F. Lloret, M. Andruh, CrysEngComm, 2014, issue 3;
“An original 3D coordination polymer constructed from trinuclear nodes and tetracarboxylato spacers”, A. S. Dinca, A. Dogaru, A. E. Ion, S. Nica, D. Dumitrescu, S. Shova, F. Lloret, M. Julve, M. Andruh, CrysEngComm, 2021, issue 6;
"Halogen bonded supramolecular assemblies constructed from azulene derivatives and perfluorinated di-/triiodobenzenes, A. Dogaru, A. A. Apostol, C. Maxim, M. Raduca, A. S. Novikov, A. Nicolescu, C. Deleanu, S. Nica, M. Andruh, CrystEngComm, 2023, issue 37"
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“New Cyanido-Bridged Heterometallic 3d-4f 1D Coordination Polymers: Synthesis, Crystal Structures and Magnetic Properties”, D. Dragancea, Gh. Novitchi, A. M. Mădălan, M. Andruh, Magnetochemistry, 2021, Volume 7, Issue 6.
1. Design, Synthesis, and Biological Evaluation of New Azulene-Containing Chalcones, D. Bala, L.-I. Jinga, M. Popa, A. Hanganu, M. Voicescu, C. Bleotu, L. Tarko, S. Nica, Materials, 2022, 15, 1629, DOI: 10.3390/ma15051629.
2. Trinuclear cyanido-bridged MII-WV complexes (M= Mn, Co): Crystal structures and magnetic properties, D. Dragancea, Gh. Novitchi, A. M Madalan, M.-G. Alexandru, S. Shova, M. Andruh, Polyhedron, 2022, 220, 115839, DOI: 10.1016/j.poly.2022.115839.
3. A New Nitronyl-nitroxide Ligand for Designing Binuclear LnIII Complexes: Syntheses, Crystal Structures, Magnetic and EPR Studies, M. Răducă, D. O. T. A. Martins, C. A. Spinu, M. Hillebrand, F.Tuna, G. Ionita, A. M. Madalan, C. Lecourt, J.-P. Sutter, M. Andruh, Eur. J. Inorg.Chem. 2022, DOI: 10.1002/ejic.202200128
4. An original 3D coordination polymer constructed from trinuclear nodes and tetracarboxylato spacers, A. S. Dinca, A. Dogaru, A. E. Ion, S. Nica, D. Dumitrescu, S. Shova, F. Lloret, M. Julve, M. Andruh, CrystEngComm., 2021, 23, 1332, DOI: 10.1039/D0CE01667E
5. Synthesis, crystal structure, magnetic, spectroscopic, and theoretical investigations of two new nitronyl-nitroxide complexes, C. A. Spinu, C. Pichon, G. Ionita, T. Mocanu, S. Calancea, M. Raduca, J. P. Sutter, M. Hillebrand, M. Andruh, J. Coord. Chem. 2021, 74, 279, DOI:10.1080/00958972.2021.1871900
6. Organic co-crystals of 1,3-bis (4-pyridyl) azulene with a series of hydrogen-bond donors, A. E. Ion, A. Dogaru, S. Shova, A. M. Madalan, O. Akintola, S. Ionescu, M. Voicescu, S. Nica, A. Buchholz, W. Plass, M. Andruh, CrystEngComm., 2018, 20, 4463, DOI: 10.1039/C8CE00945G
7. Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2, 2′: 6′, 2″-terpyridines, A. E. Ion, L. Cristian, M. Voicescu, M. Bangesh, A. M. Madalan, D. Bala, C. Mihailciuc, S. Nica, Beilstein J. Org. Chem., 2016, 12, 1812, DOI: 10.3762/bjoc.12.171
8. Visible-light triggered photoswitching systems based on fluorescent azulenyl-substituted dithienylcyclopentenes, E. A. Dragu, A. E. Ion, S. Shova, D. Bala, C. Mihailciuc, M. Voicescu, S. Ionescu, S. Nica, RSC Adv., 2015, 5, 63282 , DOI: 10.1039/C5RA11974J
9. Two-Dimensional Coordination Polymers Constructed Using, Simultaneously, Linear and Angular Spacers and Cobalt(II) Nodes. New Examples of Networks of Single-Ion Magnets, A. E. Ion, S. Nica, A. M. Madalan, S. Shova, J. Vallejo, M. Julve, F. Lloret, M. Andruh., Inorg. Chem., 2015, 54, 16, DOI: 10.1021/ic5025197
10. A chimeric design of heterospin 2p–3d, 2p–4f, and 2p–3d–4f complexes using a novel family of paramagnetic dissymmetric compartmental ligands, A. A. Patrascu, S. Calancea, M. Briganti, S. Soriano, A. M. Madalan, R. A. Allao Cassaro, A. Caneschi, F. Totti, M. G. F. Vaz, M. Andruh, Chem Commun., 2017, 53, 6504, DOI: 10.1039/C7CC03236F
11. SMM behavior tuned by an exchange coupling LEGO® approach for chimeric compounds: First 2p-3d-4f hetero-tri-spin complexes with different metal ions bridged by one aminoxyl group, A. A. Patrascu, M. Briganti, S. Soriano, S. Calancea, R. A. Allão Cassaro, F. Totti, M. G. F. Vaz, M. Andruh, Inorg. Chem., 2019, 58, 13090, DOI: 10.1021/acs.inorgchem.9b01998.
12. One-dimensional coordination polymers constructed from binuclear 3d–4f nodes and isonicotinato spacer, A. A. Patrascu, S. Calancea, R. A. Allão Cassaro, S. Soriano, A. M. Madalan, C. Maxim, M. A. Novak, M. G. F. Vaz, M. Andruh, CrystEngComm, 2016, 18, 4779. DOI: 10.1039/C6CE00729E
Bringing together quantum sieving process and new metal-organic frameworks synthesis to develop a new hydrogen isotope separation- PN-III-P2-2.1-PED-2019-2079 (contract 469PED/2020) - https://www.chimie.unibuc.ro/cercetare/anorganica/HYSO-MOF/HYSO-MOF.pdf
Project abstract: Development of new cost-effective, non-polluting technology for isotopologue sieving using porous metal-organic framework (MOF) assembled starting from rationally selected building blocks is highly desirable in modern material science.
Recently, MOFs systems have been investigated for their H2/D2 separation ability, explained through a chemical quantum sieving (CAQS) mechanism. In contrast to the vast majority of porous coordination polymers reported so far, the 3D MOF structure assembled in our group starting from binuclear nodes, hexamethylenetetramine and mandelic acid as spacers, 3∞[Cu2(mand)2(hmt)]·H2O, was synthesized using classical reaction conditions and cheap materials.
Moreover, this structure exhibits permanent porosity, thermal stability and due to its texture, good capability of H2 capturing and storage. Taking into consideration these important properties, we propose this compound as candidate in development of a hydrogen isotope separation technology. In quantum sieving, the pore size plays an important role in determining the diffusion kinetics and thereby overall separation process. In this regard, we intent to first scrutinize the ability of Zn(II) metal ion as metallic center within an isostructural metal-organic framework to efficiently separate the hydrogen isotopes. Secondly, we will focus on the modification of pore dimension and of termic stability through screening of organic components, in order to develop families of MOFs with structures and properties that can be predicted a priori. Ultimately, for the most efficient porous material we propose to develop an innovative technology using a setup that allows the analysis of thermal desorption at low temperatures (down to 20 K) by mass spectrometry, a setup that is unique in Romania, assembled at ICSI Rm. Valcea Institute.
Design and synthesis of organic switchers, of ligands used in the synthesis of coordination compounds possessing interesting photochemical properties. Physico-chemical characterization of the obtained compounds.
The synthesis of optically active ligands based on the induction and control of axial chirality. A central research direction involves the generation of arylhydrazone derivatives employed as functional precursors in the assembly of coordination compounds exhibiting luminescent properties. The study aims to correlate the absolute configuration of the ligands with the optical response of the resulting metal–organic systems. Physicochemical characterization is performed through spectroscopic analyses.
Her scientific activity focuses on the synthesis and characterization of 3d–4f heteronuclear complexes featuring oxalato bridges via the controlled decomposition of ascorbic acid. The objective is the preparation of discrete polynuclear systems in which heteronuclear building units are interconnected by oxalato ligands, leading to well-defined structural architectures. The synthesized compounds are characterized by spectroscopic techniques, including IR, UV–Vis, and luminescence spectroscopy.
